Propylene based resin composition and use thereof

ABSTRACT

Means for solving the problems 
     The thermoplastic resin composition (X1) of the present invention comprises (A1), (B1), (C1), and optionally (D1) below:
         1 to 90 wt % of an isotactic polypropylene (A1);   9 to 98 wt % of a propylene/ethylene/α-olefin copolymer (B1) containing 45 to 89 mol % of propylene-derived structural units, 10 to 25 mol % of ethylene-derived structural units, and optionally, 0 to 30 mol % of C 4 -C 20  α-olefin-derived structural units (a1);   1 to 80 wt % of a styrene-based elastomer (C1); and   0 to 70 wt % of an ethylene/α-olefin copolymer (D1) whose density is in the range of 0.850 to 0.910 g/cm 3 , wherein (A1)+(B1)+(C1)+(D1)=100 wt %.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional application of U.S. Ser. No. 13/619,135filed Sep. 14, 2012; which is a Divisional application of U.S. Ser. No.11/642,983 filed Dec. 21, 2006; which is a Continuation application ofPCT/JP2005/021730 filed Nov. 25, 2005; which claims priority fromJapanese Application No. 2004-341316 filed Nov. 25, 2004; JapaneseApplication No. 2004-343171 filed Nov. 26, 2004; Japanese ApplicationNo. 2005-061577 filed Mar. 4, 2005; Japanese Application No. 2005-088109filed Mar. 25, 2005; Japanese Application No. 2005-091468 filed Mar. 28,2005; Japanese Application No. 2005-105470 filed Mar. 31, 2005; JapaneseApplication No. 2005-105471 filed Mar. 31, 2005; Japanese ApplicationNo. 2005-153415 filed May 26, 2005; Japanese Application No. 2005-155238filed May 27, 2005; Japanese Application No. 2005-232605 filed Aug. 10,2005; Japanese Application No. 2005-276777 filed Sep. 22, 2005; JapaneseApplication No. 2005-276776 filed Sep. 22, 2005; Japanese ApplicationNo. 2005-276778 filed Sep. 22, 2005; Japanese Application No.2005-304837 filed Oct. 19, 2005; Japanese Application No. 2005-304838filed Oct. 19, 2005; Japanese Application No. 2005-304839 filed Oct. 19,2005; and Japanese Application No. 2005-318593 filed Nov. 1, 2005. Thesubject matter of each of the above listed applications is incorporatedherein by reference in entirety.

TECHNICAL FIELD

The present invention relates to a propylene-based resin composition andthe use thereof.

More particularly, the present invention (first aspect) relates to athermoplastic resin composition, a molded article at least part of whichis made of the thermoplastic resin composition, and various articles atleast part of which is made of the thermoplastic resin composition.Still more particularly, the present invention relates to athermoplastic resin composition that has excellent mechanical propertiesand is excellent in rubber elasticity and permanent compression set notonly at normal temperature but also at high temperatures, a moldedarticle at least part of which is made of the thermoplastic resincomposition, and various articles at least part of which is made of thethermoplastic resin composition.

The present invention (second aspect) more particularly relates to athermoplastic resin composition comprising a specific propylene/α-olefincopolymer, a crosslinked product of said thermoplastic resincomposition, and a molded article thereof. Still more particularly, itrelates to a thermoplastic resin composition that can be molded at lowtemperatures and provide a molded article exhibiting well-balancedflexibility, scratch resistance, and whitening resistance, a crosslinkedproduct of the thermoplastic resin composition, and a molded articlethereof.

More particularly, the present invention (third aspect) relates to apropylene-based polymer composition and a molded article made of saidcomposition such as films, sheets, blow-molded articles,injection-molded articles, tubes, and cap liners.

More particularly, the present invention (fourth aspect) relates to anoriented film made of a polypropylene-based resin composition, and stillmore particularly to a heat-shrinkable film excellent in transparency,flexibility, impact resistance, and mechanical properties which has ahigh heat-shrink ratio but a small extent of spontaneous shrinkage atroom temperature.

The present invention (a fifth aspect) more particularly relates to apolyolefin-made decorative sheet and still more particularly to apolyolefin-made decorative sheet excellent in flexibility, scratchresistance, abrasion resistance, whitening resistance on orientation,whitening resistance on folding, wrinkle resistance, heat resistance,water resistance, compression set resistance, and mechanical strength.

The present invention (sixth aspect) more particularly relates to apropylene-based resin composition and a molded article obtained fromsaid composition. Still more particularly, the present invention relatesto a propylene-based resin composition that contains a large amount ofinorganic filler and is excellent in flexibility, mechanical strength,elongation at break, heat resistance, scratch resistance, whiteningresistance, and flame retardance, and a molded article of thecomposition.

More particularly, the present invention (seventh aspect) moreparticularly relates to a foaming material, a foam, and the use of thefoam. Still more particularly, the present invention relates to acomposition that can provide foams having a low specific gravity, a lowpermanent compression set, excellent tear strength, low resilience, andexcellent scratch resistance; a foam; and the use of the foam.

More particularly, the present invention (eighth aspect) moreparticularly relates to a soft polypropylene-based resin compositionthat has high adhesion to inorganic materials, such as metal and glass,and various plastics and can provide laminates excellent in flexibility,transparency, rubber elasticity, and scratch resistance.

More particularly, the present invention (ninth aspect) relates to asheet for sealing a solar cell between a front face member and a backsurface member that are plate or sheet made of glass or plastics.

More particularly, the present invention (tenth aspect) moreparticularly relates to an electric/electronic element-sealing sheetsuitable for sealing various electrical and electronic elements,particularly solar cells, and also relates to various applications ofthe sheet (solar cell-sealing sheets, solar cell modules, powergenerators, etc.)

BACKGROUND ART

A number of resin compositions have been developed for use in a varietyof applications. As described later, propylene-based resin compositionsare employed for some applications, but further improvements arerequested on the properties required in each application.

For instance, various materials have been used in components or partsand sheets for automobile components, industrial machine components,electrical and electronic components, building materials, and cap linerswhere rubber elasticity is required. An example of such material isvulcanized rubber. Vulcanized rubber is generally produced by kneadingrubber with crosslinkers, crosslinking auxiliaries, additives,auxiliaries, and others to prepare an unvulcanized rubber blend,followed by vulcanization with heating. Therefore, vulcanized rubberencounters problems of complicated production processes and a high cost.In addition, due to thermosetting nature, vulcanized rubber cannot berecycled.

On the other hand, vinyl chloride resin is known as a material that doesnot require vulcanization but has rubber-like properties. However, vinylchloride resin is inferior in rubber elasticity to vulcanized rubber,resulting in limited application. Recently, development of a materialsubstituting vinyl chloride resin has been awaited for reasons such asthe difficulty in incineration.

A thermoplastic elastomer is known as a polymer material that isplasticized and moldable like plastics at high temperatures whileexhibiting rubber elasticity at normal temperature. As a recyclableolefinic thermoplastic elastomer, a dynamically crosslinked product ofpolypropylene and ethylene/α-olefin copolymer is known. However, in thiscase, there is also a problem of an increased cost due to the need ofusing crosslinkers and crosslinking auxiliaries.

In order to overcome these shortcomings, Patent Document 1 proposes apolyethylene-based resin composition mainly composed of an olefinicelastomer mainly derived from ethylene and its use. However, the heatresistance is insufficient because the major component is polyethylene.

As another measure, compositions comprising propylene-based polymershave recently been studied (see Patent Document 2).

However, the composition in Patent Document 2 still has room forimprovement in mechanical properties, oil acceptance, or others. Inaddition, neither rubber elasticity nor permanent compression set athigh temperature is described in Patent Document 2.

On the other hand, as described above, a thermoplastic elastomer isknown as a polymer material that is plasticized and moldable likeplastics at high temperatures while exhibiting rubber elasticity atnormal temperature. Examples thereof include, besides the dynamicallycrosslinked product of polypropylene and ethylene/α-olefin copolymer, acomposition of polypropylene and a styrene-based elastomer (see PatentDocument 3). This material is excellent in strength, flexibility, andheat resistance, and hence, can suitably be used for cap liners andothers.

A thermoplastic olefinic elastomer comprising polypropylene andethylene/α-olefin copolymer is also used because flexibility can befurther improved (see Patent Document 4).

However, the above olefinic thermoplastic elastomers are insufficient inbalance of flexibility and scratch resistance, causing a problem thatscratch resistance and whitening resistance are deteriorated ifsufficient flexibility is attained. These are the background art for thefirst and second aspects of the present invention.

Polypropylene-based resin compositions are used in various applicationssuch as electrical and electronic components, industrial materials,furniture, stationery, convenience goods, containers and packages, toys,leisure goods, and medical articles because of their excellent heatresistance, transparency, and moldability. As a technology of improvingthe flexibility and impact resistance of polypropylene-based resincompositions, addition of various soft materials is also known.

For instance, Patent Document 5 describes that a composition composed ofa polypropylene-based resin and a specific propylene/ethylene/α-olefincopolymer elastomer is excellent in transparency and usable, forexample, for stretch films.

Patent Document 6 describes a composition composed of polypropylene anda specific α-olefin copolymer elastomer in which the propylene contentis more than 20 wt % and not more than 80 wt %, the ethylene content ismore than 10 wt % and not more than 45 wt %, and the α-olefin content ismore than 10 wt % and not more than 45 wt %.

Patent Document 7 describes a composition composed of polypropylene anda specific propylene/butene/ethylene copolymer is usable for industrialshrink films and wrap films for service.

Patent Document 8 describes, for example, that a composition composed ofamorphous propylene/butene random copolymer and crystallinepropylene-based polymer is excellent in whitening resistance on foldingand usable for molded articles, transparent boxes, and others.

Patent Document 9 describes a sheet excellent in whitening resistanceand transparency made of a composition mainly composed of astyrene-based elastomer and polypropylene.

When polypropylene is used in applications where transparency isrequired, such as stretch films, the film is sometimes required tomaintain transparency when stretched or after treated at hightemperatures.

However, the compositions in Patent Documents 5 and 6 are insufficientin whitening resistance on stretching or heating. Further, thecompositions in Patent Documents 7 and 8 are poor in strength and havedifficulties in practical use.

The composition comprising the styrene-based elastomer described inPatent Document 9 is excellent in whitening resistance, flexibility, andtransparency, but styrene-based elastomers are generally immiscible withpolypropylene, whereby molded articles of such composition are whitenedunder some service conditions. Moreover, the composition containing thestyrene-based elastomer has excellent rubber elasticity at roomtemperature, but its rubber elasticity is poor at high temperatures.These are the background art for the third aspect of the presentinvention.

As a material widely used for heat-shrinkable films, polyvinylchlorideresin and polystyrene resin are known. There is, however, concern aboutadverse effects on human bodies and environment of byproducts generatedon disposal of these resins. Therefore, development of heat-shrinkablefilms using polyolefin is now underway. Conventional heat-shrinkablefilms made of polyolefin-based resin are inferior to heat-shrinkablefilms made of vinyl chloride resin in mechanical strength and heatshrink ratio at low temperatures. In particular, when this film is usedas heat-shrinkable labels for beverage PET bottles, the film is oftensubjected to shrinking process together with a PET bottle in aheat-shrink tunnel using steam or others, and therefore, there is demandfor a heat-shrinkable film having a high shrink ratio at lowertemperatures.

Further, for separating PET bottles and label resins on recycling PETbottles, PET bottles and label resins are pulverized together andgravitationally separated in liquid phase based on the differencebetween these materials in buoyancy in water. For example, the specificgravity of polystyrene-based resin is about 1.03 to about 1.06, so thatpolystyrene-based resin sinks in water together with PET resin, whichhas a specific gravity of 1.3 to 1.5. Therefore, the label made of suchresin having a specific gravity of 1 or higher is difficult to separatefrom PET resin by the above method. For this reason, a low-temperatureheat-shrinkable film made of polyolefin having a specific gravitysmaller than 1 is awaited to be developed.

As an attempt to meet this demand, for example, Patent Document 10discloses a heat-shrinkable film obtained from crystalline polypropyleneand propylene/1-butene random copolymer. This film has a high heatshrink ratio and is excellent in transparency. However, since thepropylene/1-butene random copolymer (optionally containing 10 mol % orless of another α-olefin unit) is poor in impact resistance, the filmobtained from this copolymer is also insufficient in flexibility orimpact resistance.

Patent Document 11 discloses a heat-shrinkable film made ofpropylene/α-olefin random copolymer and petroleum resin wherein thecopolymer is obtained from propylene and a C₂-C₂₀ α-olefin and has amelting point of 40 to 115° C. as measured with a DSC. This filmpossesses a higher heat shrink ratio than the film in Patent Document10, but it is still insufficient in flexibility and impact resistance.

Patent Document 12 discloses a heat-shrinkable film having a film mainlycomposed of a propylene/α-olefin random copolymer (propylene/ethylenerandom copolymer) as an intermediate layer.

In the propylene/α-olefin random copolymer, 2 to 7 mol % of a co-monomer(ethylene or α-olefin) is copolymerized with propylene. Thepropylene/α-olefin random copolymer (propylene/ethylene randomcopolymer) alone cannot attain a sufficient heat shrink ratio, andimpact resistance of films obtained therefrom is also poor.

Patent Document 12 also discloses a technology of adding linearlow-density polyethylene and ethylene-based rubber to apropylene/α-olefin random copolymer (propylene/ethylene randomcopolymer). This technology improves heat shrink ratio and impactresistance of the film, but has a problem that film transparency islowered.

Patent Document 13 discloses that a composition consisting of 20 to 50parts by weight of polypropylene and 80 to 50 parts by weight ofpropylene/butene/ethylene copolymer is usable for stretch films andothers. However, the document does not describe film drawing or use forheat-shrinkable films. These are the background art for the fourthaspect of the invention.

As a sheet for surface decoration or protection in building materials,home electric appliances, automobile interior and exterior materials,and others, there have conventionally been used films mainly composed ofvinyl chloride resin, which have well-balanced scratch resistance,whitening resistance on folding, wrinkle resistance, transparency, andothers.

However, since such films have disadvantages such as difficulty inincineration as described above, a focus has been made in the art onpolyolefin-based materials with less burden on environment.

For instance, Patent Document 14 discloses a decorative sheet having apolypropylene film as an essential component layer. Patent Document 15discloses a decorative sheet having a thermoplastic olefinic elastomeras an essential component layer.

However, in the decorative sheet proposed in Patent Document 14, whichhas a polypropylene film as a component layer, the high crystallinityand the melting point of polypropylene cause problems such as loweringin flexibility and occurrence of cracks or whitening at bended facesduring folding processing. The decorative sheet proposed in PatentDocument 15, which has a thermoplastic olefinic elastomer as a componentlayer, is excellent in flexibility and hardly encounters cracking orwhitening at bended faces, but has problems of insufficient transparencyand mechanical strength, and others.

In order to solve these problems, Patent Document 16 proposes adecorative sheet having a layer made of a resin composition containing aspecific non-crystalline polyolefin and a crystalline polypropylene at aspecific ratio.

This decorative sheet was less liable to cracks and whitening at bendedfaces but insufficient in mechanical strength, scratch resistance, andheat resistance.

Patent Document 17 proposes a decorative sheet having a polyester filmas a surface protective layer.

Using a polyester film as a surface protective layer significantlyimproved mechanical strength and scratch resistance, but such materialcontaining a polar group in its molecular chain had a problem of poorwater resistance (resistance against water vapor permeation). These arethe background art for the fifth aspect of the invention.

Polypropylene-based resin is a more excellent material thanpolyethylene-based resin (polyethylene-based elastomer) in heatresistance, mechanical resistance, and scratch resistance, and moldedarticles obtained from polypropylene-based resin are used in variousapplications. Molded articles prepared from a conventional polypropyleneand inorganic filler are excellent in heat resistance and mechanicalstrength, but poor in flexibility and impact resistance. For thisreason, in uses where such properties as flexibility and impactresistance are required, polyethylene-based resin is mainly employed.However, the problem is that molded articles of polyethylene-based resinare insufficient in scratch resistance.

As a molded article obtained from polypropylene-based resin andinorganic filler (flame retardant), an electric cable or wire harness isknown, which requires scratch resistance. Patent Document 18 disclosesan insulated electrical wire for automobiles using a specific propylenepolymer. The molded article used in Patent Document 18 was excellent inflexibility and impact resistance but insufficient in scratchresistance. These are background art for the sixth aspect of theinvention.

As a resin material having a low specific gravity, which means light inweight, and is excellent in flexibility and mechanical strength, acrosslinked foam is widely used in building interior and exteriormaterials, automobile components such as interior materials and doorglassruns, packaging materials, convenience goods, and others. This isbecause, while mechanical strength of a resin is lowered when merelyfoamed for reducing its weight, foaming with crosslinking can attainweight reduction without lowering mechanical strength by bonding themolecular chains to each other through crosslinking reaction of theresin.

Crosslinked foams of resins are also used for footwear and footwearcomponents, for example, shoe soles (mainly mid-soles) for sports shoesand others. This results from demand for a material that is lightweight,less deformed in long-term use, mechanically strong enough to be durablein use under severe conditions, low resilient so as to absorb impact onlanding, and scratch resistance.

Conventionally, a crosslinked foam formed from ethylene/vinyl acetatecopolymer has been widely used for shoe soles. However, the crosslinkedfoam formed from ethylene/vinyl acetate copolymer composition has a highspecific gravity and a large permanent compression set. Therefore, whenthe foam is used for shoe soles, there are problems of heavy weight andsignificant abrasion caused by loss of mechanical strength due tocompression during long-term use.

To overcome these disadvantages, Patent Documents 19 and 20 disclose acrosslinked foam obtained from ethylene/α-olefin copolymer and acrosslinked foam obtained from a mixture of ethylene/vinyl acetatecopolymer and ethylene/α-olefin copolymer, respectively. In these foams,the specific gravity and permanent compression set are reduced, butsatisfactory performances have not been attained.

As a material obtained by dynamic crosslinking of olefinic rubber, athermoplastic elastomer is known (see Patent Document 21). However,Patent Document 21 does not suggest foaming. In addition, it isdifficult to foam the thermoplastic olefinic elastomer at a high foamingratio for providing foams with a low specific gravity. Therefore, thethermoplastic olefinic elastomer is not suitable for the aboveapplications.

As described above, it has been hard to obtain foams having low specificgravity, low permanent compression set (CS), excellent tear strength,low resilience, and good scratch resistance. These are the backgroundart for the seventh aspect of the invention.

Since films or sheets of soft polypropylene-based resin are superior tothose of soft polyethylene-based resin in heat resistance, flexibility,and mechanical strength, it is expected that their use will be developedin automobile components, building materials, food industry, and others.In these fields, the film or sheet is used as laminates with inorganicmaterial, such as metal (including aluminum, copper, iron, stainlesssteel, etc.) and glass, or various plastics in many cases, so that thefilm or sheet is required to have excellent adhesion to variousmaterials. In particular, soft polypropylene-based resin that exhibitsadhesion to inorganic materials such as metal has been awaited.

It is difficult to graft polypropylene-based resin with a polar monomerusing an organic peroxide or the like, and such grafting greatlydecreases the molecular weight, significantly lowering heat resistanceand mechanical properties.

Patent Document 22 describes a technology of adding an organosiliconcompound to polypropylene for improving adhesion to metal and others.However, the laminate obtained using this technology is poor intransparency, flexibility, and rubber elasticity, and hence, its use islimited. The polyethylene resin obtained by this technology has improvedadhesion as compared with conventional unmodified polypropylene.However, the polypropylene-based resin obtained by this technology hadhigh crystallinity, and therefore, it was sometimes easily peeled offsince peeling stress was concentrated when peeling. These are thebackground art of the eighth aspect of the invention.

In conventional sheets for sealing a solar cell between front and backplates or sheets made of glass, plastics, or others (solar cell-sealingsheet), ethylene/vinyl acetate copolymer (in this specification, oftenabbreviated as “EVA”) has been commonly used. This is because EVA isflexible and highly transparent and provides long-term durability whenblended with appropriate additives such as a weathering stabilizer andan adhesion promoter.

However, EVA has a low melting point, causing problems in heatresistance such as thermal deformation at environmental temperatureswhere solar cell modules are used. To resolve this problem, acrosslinked structure is formed by adding an organic peroxide to impartheat resistance.

Solar cell-sealing sheets are prepared by a known sheet molding processapplicable to molding polyolefin. There has been a problem that additionof an organic peroxide disables high-speed production becauselow-temperature molding is inevitable to avoid decomposition of theorganic peroxide.

The production process of a solar cell module configured as (glass orplastics)/(solar cell-sealing sheet)/(solar cell)/(solar cell-sealingsheet)/(back sheet) generally includes two steps: a temporary bondingstep by vacuum heat lamination and a crosslinking step using ahigh-temperature oven. Since the crosslinking step using the organicperoxide takes several tens of minutes, omitting or speed-up of thecrosslinking step is strongly required.

In long-term use of solar cells, gas generated by decomposition of EVA(acetic acid gas) or the vinyl acetate group in EVA itself may haveadverse effects on the solar cell and lower its power generationefficiency.

To resolve such problems, a solar cell-sealing sheet usingethylene/α-olefin copolymer has been proposed (see Patent Document 23).With the proposed materials, the adverse effects on solar cell elementsare considered to decrease, but balance of heat resistance andflexibility is insufficient. Furthermore, the crosslinking is hard toomit since desirable heat resistance is not attained withoutcrosslinking. These are the background art for the ninth aspect of theinvention.

Recent advancement in electrical/electronics elements is remarkable, andthey have been widely used in every aspect of social, industrial, anddomestic circumstances. Generally, electrical/electronics elements areeasily affected by moisture, oxidants, and others, and hence, they aresealed in many applications to attain stable operation and long servicelife.

Nowadays, various materials for sealing electrical/electronics elementsare produced and supplied in the market. Among them, a sealing sheetmade of an organic polymer is very useful because of its applicabilityto relatively wide area and ease in use. In addition, transparency canbe attained relatively easily, and hence, the sealing sheet isparticularly suitable for sealing electrical/electronics elements usinglight, especially solar cells.

Solar cells are generally used in sealed solar cell modules, becausethey are used outdoors such as on the roof of buildings in many cases.The solar cell module has a structure in which a solar cell element madeof polycrystalline silicon or others is sandwiched between solarcell-sealing materials made of a soft transparent resin to form a stack,of which the front and back surfaces are covered with solar cell moduleprotective sheets. That is, a typical solar cell module has a layeredstructure, solar cell module protective sheet (front protectivesheet)/solar cell-sealing sheet/solar cell element/solar cell-sealingsheet/solar cell module protective sheet (back protective sheet). Owingto this structure, the solar cell module has weatherability and issuitable for use outdoors such as on the roof of buildings.

As a material forming the solar cell-sealing sheet (solar cell-sealingmaterial), ethylene-vinyl acetate copolymer (EVA) has been widely usedfrom the viewpoint of transparency, flexibility, or others as describedabove (for example, see Patent Document 24). When used as the solarcell-sealing material, EVA is generally crosslinked to attain heatresistance. However, the crosslinking takes a relatively long time ofabout one to two hours, lowering the production speed and productivityof solar cell elements. Further, there has been a concern about possibleadverse effects of acetic acid gas or other chemicals generated bydecomposition of EVA on solar cell modules.

As one of the methods for solving the above-mentioned technicalproblems, use of a solar cell-sealing sheet made of non-crosslinkedresin has been proposed (for example, see Patent Document 25). However,with an increase in requested levels of the productivity, durabilityunder severe conditions, and service life of solar cells, all of thetransparency, heat resistance, and flexibility have become required tohave levels higher than those attainable with EAA, EMAA, or other resinsproposed specifically in Patent Document 25. If such a request issatisfied, the sealing sheet would be quite useful forelectrical/electronics elements besides solar cells.

When the sealing sheet is used for solar cell modules and others, sincethe sheet is laminated with glass or others in many cases, adhesion toglass and others is practically important. Some conventional sealingsheets have insufficient adhesion to glass and others, and hence, theimprovement has been strongly desired. These are the background art forthe tenth aspect of the present invention.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-088164

Patent Document 2: Japanese Patent Laid-Open Publication No. H08-302093Patent Document 3: Japanese Patent Laid-Open Publication No. H07-076360Patent Document 4: Japanese Patent Laid-Open Publication No. H11-349753Patent Document 5: Japanese Patent Laid-Open Publication No. H08-302093Patent Document 6: Japanese Patent Laid-Open Publication No. H08-113681

Patent Document 7: Japanese Patent Laid-Open Publication No. 2002-348417Patent Document 8: Japanese Patent Laid-Open Publication No. 2005-47944

Patent Document 9: Japanese Patent Laid-Open Publication No. H08-269271Patent Document 10: Japanese Patent Laid-Open Publication No. H09-278909

Patent Document 11: Japanese Patent Laid-Open Publication No.2003-306587 Patent Document 12: Japanese Patent Laid-Open Publication2002-234115

Patent Document 13: Japanese Patent Laid-Open Publication No. H08-302093Patent Document 14: Japanese Patent Laid-Open Publication No. H06-198830Patent Document 15: Japanese Patent Laid-Open Publication No. H06-16832

Patent Document 16: Japanese Patent Laid-Open Publication No.2000-281807

Patent Document 17: Japanese Patent Laid-Open Publication No. H10-258488

Patent Document 18: Japanese Patent Laid-Open Publication No.2003-313377

Patent Document 19: Unexamined Patent Application Publication No.H09-501447Patent Document 20: Japanese Patent Laid-Open Publication No. H11-206406

Patent Document 21: Japanese Patent Laid-Open Publication No.2001-171439 Patent Document 22: Japanese Patent Laid-Open PublicationNo. 2003-201375 Patent Document 23: Japanese Patent Laid-OpenPublication No. 2000-91611

Patent Document 24: Japanese Patent Laid-Open Publication No. H08-283696

Patent Document 25: Japanese Patent Laid-Open Publication No.2001-068703 DISCLOSURE OF THE INVENTION Problems to be Solved by theInvention

An object of the present invention is to provide propylene-based resincompositions suitable for use in various applications and the usethereof.

An object of the first aspect of the invention to solve theabove-mentioned problems is to provide a resin composition that isexcellent in mechanical properties and excellent in rubber elasticityand permanent compression set not only at normal temperature but also athigh temperatures, a molded article obtained using the composition, andthe use thereof.

An object of the second aspect of the invention to solve theabove-mentioned problems is to provide a thermoplastic resin compositionhaving excellent balance of flexibility and scratch resistance and goodwhitening resistance, a crosslinked product obtained by crosslinking thethermoplastic resin composition, and a molded article with well-balancedflexibility and scratch resistance as well as excellent whiteningresistance.

An object of the third aspect of the invention to solve theabove-mentioned problems is to provide a propylene-based polymercomposition that is particularly excellent in mechanical strength,transparency, and whitening resistance (on orientation and heattreatment) and also excellent in impact resistance, scratch resistance,flexibility, transparency, stretching property, room-temperature rubberelasticity, and high-temperature rubber elasticity; and a molded articleof the composition.

An object of the fourth aspect of the invention is to provide a filmexcellent in shrinking properties (high shrink ratio on heating andreduced spontaneous shrink at room temperature), transparency,flexibility, stretching property, and impact resistance, and aheat-shrinkable film using the film; and another object is to provide aresin composition suitable for use in the film and the heat-shrinkablefilm.

An object of the fifth aspect of the invention is to provide apolyolefin-based decorative sheet excellent in flexibility, scratchresistance, abrasion resistance, whitening on orientation, whitening onfolding, wrinkle resistance, heat resistance, water resistance,compression set resistance, and mechanical strength.

An object of the sixth aspect of the invention is to provide apropylene-based resin composition that contains a large amount of aninorganic filler and is excellent in flexibility, mechanical strength,elongation at break, heat resistance, scratch resistance, whiteningresistance, and flame retardance. Another object of the sixth aspect ofthe invention is to provide a method for producing a propylene-basedresin composition excellent in flexibility, mechanical strength,elongation at break, heat resistance, whitening resistance, and flameretardance, and especially in scratch resistance; and a propylene-basedpolymer composition suitable for use in producing the resin composition.Still another object of the sixth aspect of the invention is to providea molded article made of the above composition and an electrical wirehaving an insulator and/or a sheath made of the composition.

An object of the seventh aspect of the invention is to provide amaterial for foam capable of providing a foam excellent in tearstrength, low resilience, and scratch resistance and a foam made of thematerial.

An object of the eighth aspect of the invention is to provide a softpolypropylene-based resin composition that has high adhesion toinorganic materials, such as metal and glass, and various plastics andcan form a laminate excellent in flexibility, transparency, rubberelasticity, and scratch resistance.

An object of the ninth aspect of the invention to solve theabove-mentioned problems is to provide a solar cell-sealing sheet usinga soft propylene-based material that is newly introduced into thesefields, specifically to provide a solar cell-sealing sheet that causesno gas resulting from decomposition of the raw material, and hence, hasno adverse effect on solar cell elements and exhibits excellentmechanical strength, solar cell sealing ability, transparency,weatherability, and heat resistance even without crosslinking.

An object of the tenth aspect of the invention to solve theabove-mentioned problems is to provide an electrical/electronicselement-sealing sheet that is suitable for protecting solar cells andvarious electrical/electronics elements and excellent in transparency,heat resistance, and flexibility. Another object of the tenth aspect ofthe invention is to further impart excellent adhesion, which isessential in practical use, to the excellent electrical/electronicselement-sealing sheet.

Means for Solving the Problems

The present inventors have studied intensively to solve the aboveproblems and accomplished the present invention.

Namely, thermoplastic resin composition (X1) according to the firstaspect of the invention comprises (A1), (B1), (C1), and if necessary,(D1) below:

1 to 90 wt % of isotactic polypropylene (A1);

9 to 98 wt % of propylene/ethylene/α-olefin copolymer (B1) containing 45to 89 mol % of propylene-derived structural units, 10 to 25 mol % ofethylene-derived structural units, and if necessary, 0 to 30 mol % ofC₄-C₂₀ α-olefin-derived structural units (a1);

1 to 80 wt % of styrene-based elastomer (C1); and

0 to 70 wt % of ethylene/α-olefin copolymer (D1) having a density of0.850 to 0.910 g/cm³;

wherein (A1)+(B1)+(C1)+(D1)=100 wt %.

Thermoplastic resin composition (X1) according to the first aspect ofthe invention preferably further contains softener (E1) in an amount of1 to 400 parts by weight relative to 100 parts by weight of the total of(A1)+(B1)+(C1)+(D1).

The molded article of the first aspect of the invention has at least oneportion made of thermoplastic resin composition (X1).

The molded article of the first aspect of the invention is preferably afilm or sheet.

The molded article of the first aspect of the invention is preferably amono-filament, a fiber, or a nonwoven fabric.

The automobile interior or exterior component of the first aspect of theinvention has at least one portion made of thermoplastic resincomposition (X1).

The home electric appliance component of the first aspect of theinvention has at least one portion made of thermoplastic resincomposition (X1).

The construction or building component of the first aspect of theinvention has at least one portion made of thermoplastic resincomposition (X1).

The packaging sheet or cap liner of the first aspect of the inventionhas at least one portion made of thermoplastic resin composition (X1).

The cap of the first aspect has the above cap liner.

The packaging container of the first aspect of the invention has theabove cap.

The gasket of the first aspect of the invention has at least one portionmade of the thermoplastic resin composition (X1).

The daily-use product of the first aspect of the invention have at leastone portion made of thermoplastic resin composition (X1).

The decorative sheet of the first aspect has at least one portion madeof thermoplastic resin composition (X1).

Thermoplastic resin composition (X2) according to the second aspect ofinvention comprises (A2), (B2), (C2), (D2), and (E2) below:

5 to 95 wt % of propylene/α-olefin copolymer (B2) whose melting point isnot higher than 100° C. or not observed when measured with adifferential scanning calorimeter (DSC);

5 to 95 wt % of styrene-based elastomer (C2);

0 to 90 wt % of isotactic polypropylene (A2);

0 to 70 wt % of ethylene/α-olefin copolymer (D2) having a density of0.850 to 0.910 g/cm³;

wherein (A2)+(B2)+(C2)+(D2)=100 wt %, and

softener (E2) in an amount of 0 to 400 parts by weight relative to 100parts by weight of the total of (A2)+(B2)+(C2)+(D2).

In thermoplastic resin composition (X2) according to the second aspectof the invention, propylene/α-olefin copolymer (B2) is preferably acopolymer of propylene and at least one C₄-C₂₀ α-olefin.

In thermoplastic resin composition (X2) according to the second aspectof the invention, propylene/α-olefin copolymer (B2) is preferably apropylene/1-butene copolymer with a molecular weight distribution(Mw/Mn) of 3 or less as measured by gel permeation chromatography (GPC).

In thermoplastic resin composition (X2) according to the second aspectof the invention, propylene/α-olefin copolymer (B2) is preferablyproduced by polymerization using a metallocene catalyst.

The crosslinked product of thermoplastic resin composition (X2) of thesecond aspect of the invention is obtained by crosslinking thermoplasticresin composition (X2).

The molded article of the second aspect of the invention is made ofthermoplastic resin composition (X2).

The molded article of the second aspect of the invention is made of theabove crosslinked product.

The molded article of the second aspect of the invention is obtained byfurther crosslinking the above molded article.

Propylene-based polymer composition (X3) according to the third aspectof the invention comprises

10 to 98 wt % of propylene-based polymer (A3) that contains 90 mol % ormore of propylene-derived structural units, is insoluble in n-decane at23° C., and has an intrinsic viscosity [η] of 0.01 to 10 dl/g asmeasured in decalin at 135° C.; and

2 to 90 wt % of soft propylene/α-olefin random copolymer (B3) satisfyingall of requirements (b1) to (b5) below:

(b1) the intrinsic viscosity [η] measured in decalin at 135° C. is 0.01to 10 dl/g;

(b2) the melting point is not higher than 100° C. or not observed whenmeasured with a DSC;

(b3) the content of propylene-derived structural units is 60 to 75 mol%, the content of ethylene-derived structural units is 10 to 14.5 mol %,and the content of C₄-C₂₀ α-olefin-derived structural units is 10.5 to30 mol % (wherein the total of propylene-derived structural units,ethylene-derived structural units, and C₄-C₂₀ α-olefin-derivedstructural units is 100 mol %);

(b4) the triad tacticity (mm-fraction) measured with ¹³C-NMR is 85% to97.5%; and

(b5) the molecular weight distribution (Mw/Mn) measured by gelpermeation chromatography (GPC) is 1.0 to 3.0.

In propylene-based polymer composition (X3) according to the thirdaspect of the invention, the melting point of propylene-based polymer(A3) is preferably 110 to 170° C. as measured with a differentialscanning calorimeter (DSC).

Preferably, propylene-based polymer composition (X3) according to thethird aspect of the invention further contains at least one polymer (C3)that is selected from an ethylene-based polymer and a styrene-basedpolymer and has a Shore A hardness of 95 or less and/or a Shore Dhardness of 60 or less, wherein the total of component(s) (C3) is in therange of 1 to 40 parts by weight relative to 100 parts by weight of thetotal of propylene-based polymer (A3) and soft propylene/α-olefin randomcopolymer (B3).

In a preferred embodiment of the propylene-based polymer composition(X3) according to the third aspect of the invention, the intensites ofmagnetization in decay process due to transverse relaxation forpropylene-based polymer (A3), soft propylene/α-olefin random copolymer(B3), and propylene-based polymer composition (X3-1) described below,each of which is measured with pulse NMR (solid-echo experiment,observed for ¹H) up to 1000 μs, satisfy relation (3-1) below in theentire range of t (observing time) from 500 to 1000 μs.

M(t)_(A)×(1−f _(B))+M(t)_(B) ×f _(B) −M(t)_(X-1)≧0.02  3-1

M (t)_(A): intensity of magnetization in decay process at time tmeasured for propylene-based polymer (A3) used in propylene-basedpolymer composition (X3),

M (t)_(B): intensity of magnetization in decay process at time tmeasured for soft propylene/α-olefin random copolymer (B3) used inpropylene-based polymer composition (X3),

M(t)_(X-1): intensity of magnetization in decay process at time tmeasured for propylene-based polymer composition (X3-1) prepared bymelt-kneading a polypropylene containing propylene-based polymer (A3)used in propylene-based polymer (X3) with soft propylene/α-olefin randomcopolymer (B3) used in propylene-based polymer (X3) in such a ratio thatthe weight ratio of polymer (A3) to copolymer (B3) in composition (X3-1)is identical to the ratio in propylene-based polymer composition (X3),and

f_(B): weight ratio of soft propylene/α-olefin random copolymer (B3) tothe total of propylene-based polymer (A3) and soft propylene/α-olefinrandom copolymer (B3) in propylene-based polymer composition (X3);0.02≦f_(B)≦0.90, wherein t (observation time) is 500 to 1000 μs;M(t)_(A), M(t)_(B), and M(t)_(X-1) are each normalized as 0 to 1 (themaximum intensity is set to be 1).

The molded article of the third aspect of the invention is made ofpropylene-based polymer composition (X3).

The molded article of the third aspect is preferably any of a film, asheet, a blow-molded article, an injection-molded article, and a tube.

The cap liner of the third aspect of the invention has at least onelayer of propylene-based polymer composition (X3).

The wrap film for foods of the third aspect of the invention has atleast one layer made of propylene-based polymer composition (X3).

The wrap film for foods of the third aspect of the invention comprisespreferably a laminate having at least one layer made of propylene-basedpolymer composition (X3) and at least one layer made of an ethylenehomopolymer or an ethylene copolymer containing 70 mol % or more ofethylene units.

The single-layer or multilayer film according to the fourth aspect ofinvention has at least one layer that is made of resin composition (X4)comprising (A4) and (B4) below and monoaxially or biaxially oriented:

10 to 97 wt % of isotactic polypropylene (A4); and

3 to 90 wt % of propylene/ethylene/α-olefin copolymer (B4) that contains40 to 85 mol % of propylene-derived structural units, 5 to 30 mol % ofethylene-derived structural units, and 5 to 30 mol % of C₄-C₂₀α-olefin-derived structural units (a4), the melting point of (B4) beingnot higher than 100° C. or not observed when measured with adifferential scanning calorimeter, wherein the total of (A4) and (B4) is100 wt %.

In the single-layer or multilayer film according to the fourth aspect ofthe invention, resin composition (X4) preferably contains hydrocarbonresin (C4) having a softening point of 50° C. to 160° C. as measuredwith the ring-and-ball method and a number-average molecular weight of300 to 1400 as measured by gel permeation chromatography (GPC) in anamount of 3 to 70 parts by weight relative to 100 parts by weight of thetotal of (A4)+(B4).

The heat-shrinkable film of the fourth aspect of the invention comprisesthe above film.

The resin composition (X4) according to the fourth aspect of theinvention comprises

10 to 97 wt % of an isotactic polypropylene (A4);

3 to 90 wt % of a propylene/ethylene/α-olefin copolymer (B4) thatcontains 40 to 85 mol % of a propylene-derived structural units, 5 to 30mol % of an ethylene-derived structural units, and 5 to 30 mol % of aC₄-C₂₀ α-olefin-derived structural units (a4), the melting point of (B4)being not higher than 100° C. or not observed when measured with adifferential scanning calorimeter, wherein the total of (A4) and (B4) is100 wt %; and

A hydrocarbon resin (C4) having a softening point of 50° C. to 160° C.as measured with the ring-and-ball method and a number-average molecularweight of 300 to 1400 as measured by gel permeation chromatography (GPC)in an amount of 3 to 70 parts by weight relative to 100 parts by weightof the total of (A4)+(B4).

The polyolefin decorative sheet according to the fifth aspect ofinvention has at least one component layer made of propylene-basedpolymer composition (X5) that contains

isotactic polypropylene (A5) and propylene-based polymer (B5) whosemelting point is not higher than 120° C. or not observed when measuredwith a differential scanning calorimeter (DSC), wherein

the amount of (A5) is 10 to 99 parts by weight and the amount of (B5) is1 to 90 parts by weight based on 100 parts by weight of the total of(A5) and (B5).

In the polyolefin decorative sheet according to the fifth aspect,propylene-based polymer composition (X5) preferably contains at leastone soft polymer (C5) other than propylene-based polymer (B5) having aShore A hardness of 95 or less and/or a Shore D hardness of 60 or lessin an amount of 1 to 80 parts by weight relative to 100 parts by weightof the total of (A5) and (B5).

In the polyolefin decorative sheet according to the fifth aspect of theinvention, the layer made of propylene-based polymer composition (X5) ispreferably used as a protective layer.

Preferably, the polyolefin decorative sheet according to the fifthaspect of the invention further has at least one component layer made ofa polyolefin-based resin composition other than propylene-based polymercomposition (X5).

In the polyolefin decorative sheet according to the fifth aspect of theinvention, the layer made of propylene-based polymer composition (X5)and the layer made of a polyolefin-based resin composition other thanpropylene-based polymer composition (X5) are preferably laminatedwithout intervening of any adhesive therebetween.

Propylene-based resin composition (X6) according to the sixth aspect ofthe present invention contains

0 to 80 wt % of propylene-based polymer (A6) whose melting point is 120to 170° C. as measured with a differential scanning calorimeter (DSC);

5 to 85 wt % of propylene-based polymer (B6) whose melting point is nothigher than 120° C. or not observed when measured with a differentialscanning calorimeter (DSC);

0 to 40 wt %, as total, of one or more elastomer (C6) selected fromethylene-based elastomer (C6-1) and styrene-based elastomer (C6-2); and

15 to 80 wt % of inorganic filler (D6), wherein the total of components(A6), (B6), (C6), and (D6) is 100 wt %.

In propylene-based resin composition (X6) according to the sixth aspectof the invention, propylene-based polymer (B6) is preferablypropylene/C₄-C₂₀ α-olefin random copolymer (B6-1) satisfyingrequirements (a) and (b) below:

-   -   (a) the molecular weight distribution (Mw/Mn) measured by gel        permeation chromatography (GPC) is 1 to 3; and    -   (b) the melting point, Tm (° C.), and the content of        co-monomer-derived structural units, M (mol %), determined from        ¹³C-NMR spectrum measurement satisfy the relation,

146exp(−0.022 M)≧Tm≧125exp(−0.032 M),

wherein Tm is lower than 120° C.

In propylene-based resin composition (X6) according to the sixth aspectof the invention, propylene-based polymer (B6) is preferablypropylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2) satisfyingrequirements (m) and (n) below:

(m) the molecular weight distribution (Mw/Mn) measured by gel permeationchromatography (GPC) is 1 to 3; and

(n) the copolymer contains 40 to 85 mol % of propylene-derivedstructural units, 5 to 30 mol % of ethylene-derived structural units,and 5 to 30 mol % of C₄-C₂₀ α-olefin-derived structural units, whereinthe total of propylene-derived structural units, ethylene-derivedstructural units, and C₄-C₂₀ α-olefin-derived structural units is 100mol %.

In propylene-based resin composition (X6) according to the sixth aspect,inorganic filler (D6) is preferably at least one compound selected frommetal hydroxides, metal carbonates, and metal oxides.

Propylene-based resin composition (X6) according to the sixth aspect ofthe invention preferably contains oil (E6) in an amount of 0.1 to 20parts by weight relative to 100 parts by weight of the total ofpropylene-based polymer (A6), propylene-based polymer (B6), at least oneelastomer (C6) selected from ethylene-based elastomer (C6-1) andstyrene-based elastomer (C6-2), and inorganic filler (D6).

Propylene-based resin composition (X6) according to the sixth aspectpreferably contains graft-modified polymer (F6), in which a polargroup-containing vinyl compound is grafted in an amount of 0.01 to 10 wt% based on 100 wt % of the graft-modified polymer, in an amount of 0.1to 30 parts by weight relative to 100 parts by weight of the total ofpropylene-based polymer (A6), propylene-based polymer (B6), at least oneelastomer (C6) selected from ethylene-based elastomer (C6-1) andstyrene-based elastomer (C6-2), and inorganic filler (D).

In the method for producing propylene-based resin composition (X6)according to the sixth aspect of the invention, propylene-based polymer(B6) and graft-modified polymer (F6) are melt-kneaded to producepropylene-based polymer composition (G6), and said propylene-basedpolymer composition (G6) is melt-kneaded with components includinginorganic filler (D6), optionally propylene-based polymer (A6), andoptionally at least one elastomer (C6) selected from ethylene-basedelastomer (C6-1) and styrene-based elastomer (C6-2).

Propylene-based resin composition (X6) of the sixth aspect of theinvention is produced by the above method.

Propylene-based polymer composition (G′6) according to the sixth aspectof the invention comprises

99 to 14 parts by weight of propylene-based polymer (B6) whose meltingpoint is lower than 120° C. or not observed when measured with adifferential scanning calorimeter (DSC); and

1 to 86 parts by weight of graft-modified polymer (F6) in which a polargroup-containing vinyl compound is grafted in an amount of 0.01 to 10 wt% based on 100 wt % of the graft-modified polymer.

Propylene-based polymer composition (G′6) according to the sixth aspectof the invention preferably contains 99 to 50 parts by weight ofpropylene-based polymer (B6) and 1 to 50 parts by weight ofgraft-modified polymer (F6).

The molded article of the sixth aspect of the invention is made ofpropylene-based resin composition (X6).

The molded article of the sixth aspect of the invention is preferably aninsulator or a sheath in an electrical wire.

The electrical wire of the sixth aspect of the invention has aninsulator made of the propylene-based resin composition (X6) and/or asheath made of the propylene-based resin composition (X6).

The electrical wire of the sixth aspect of the invention is preferablyan electrical wire for automobiles or apparatuses.

Material for foam (X7) according to the seventh aspect of the inventioncontains propylene-based polymer (B7) whose melting point is lower than100° C. or not observed when measured with a differential scanningcalorimeter.

Material for foam (X7) according to the seventh aspect of the inventionpreferably contains the propylene-based polymer (B7) that is a copolymerof propylene and at least one C₂-C₂₀ α-olefin except propylene and themelting point of the copolymer is lower than 100° C. or not observedwhen measured with a differential scanning calorimeter.

The material for foam (X7) according to the seventh aspect of theinvention is preferably a composition containing 30 to 100 parts byweight of propylene-based polymer (B7) and 0 to 70 parts by weight ofpropylene-based polymer (A7) having a melting point of 100° C. or higheras measured with a differential scanning calorimeter, wherein the totalof (B7) and (A7) is 100 parts by weight.

Material for foam (X7) according to the seventh aspect of the inventionis preferably a composition containing 1 to 1900 parts by weight ofethylene/α-olefin copolymer (C7) and/or 1 to 1900 parts by weight ofethylene/polar monomer copolymer (D7) relative to 100 parts by weight ofthe total of propylene-based polymer (B7) and, optional propylene-basedpolymer (A7).

In material for foam (X7) according to the seventh aspect of theinvention, propylene-based polymer (B7) is preferablypropylene/ethylene/α-olefin copolymer (B7-1) containing 45 to 92 mol %of propylene-derived structural units, 5 to 25 mol % of ethylene-derivedstructural units, and 3 to 30 mol % of C₄-C₂₀ α-olefin-derivedstructural units, wherein the total of propylene-derived structuralunits, ethylene-derived structural units, and C₄-C₂₀ α-olefin-derivedstructural units is 100 mol %.

Material for foam (X7) according to the seventh aspect of the inventionpreferably further contains a foaming agent (E7).

In material for foam (X7) according to the seventh aspect of theinvention, ethylene/α-olefin copolymer (C7) is preferablyethylene/1-butene copolymer.

The foam of the seventh aspect is obtained from material for foam (X7).

The foam of the seventh aspect of the invention is preferably obtainedby heat treatment or radiation treatment of material for foam (X7).

The foam of the seventh aspect of the invention is preferably obtainedby heat treatment of material for foam (X7) placed in a mold.

The foam of the seventh aspect of the invention is preferably obtainedby secondary compression of the above foam.

The foam of the seventh aspect of the invention preferably has a gelcontent of 70% or more and a specific gravity of 0.6 or less.

The laminate of the seventh aspect of the invention has a layercomprising the above foam and a layer made of at least one materialselected from polyolefin, polyurethane, rubber, leather, and artificialleather.

The footwear of the seventh aspect of the invention comprises the abovefoam or the above laminate.

The footwear component of the seventh aspect of the invention comprisesthe above foam or laminate.

The footwear component is preferably a mid sole, an inner sole, or asole.

Resin composition (X8) according to the eighth aspect of the inventioncontains

a thermoplastic resin composition containing

0 to 90 wt % of propylene-based polymer (A8) whose melting point is 100°C. or higher as measured with a differential scanning calorimeter and

10 to 100 wt % of soft propylene-based copolymer (B8) that is acopolymer of propylene and at least one C₂-C₂₀ α-olefin exceptpropylene, the Shore A hardness of (B8) being 30 to 80, the meltingpoint of (B8) being lower than 100° C. or not observed when measuredwith a differential scanning calorimeter; and

relative to 100 parts by weight of the thermoplastic resin composition(total of (A8) and (B8)),

0.1 to 10 parts by weight of coupling agent (Y8) and 0 to 5 parts byweigh of organic peroxide (Z8).

The laminate of the eighth aspect of the invention contains at least onelayer [a] containing resin composition (X8) and a layer [b] containing amaterial selected from metal, an inorganic compound, and a polar plasticmaterial on one or both surfaces of layer [a].

The solar cell-sealing sheet according to the ninth aspect of theinvention contains thermoplastic resin composition (X9) composed of 0 to70 wt % of propylene-based polymer (A9) whose melting point is 100° C.or higher as measured with a differential scanning calorimeter and 30 to100 wt % of soft propylene-based copolymer (B9) that is a copolymer ofpropylene and at least one C₂-C₂₀ α-olefin except propylene, the Shore Ahardness of (B9) being 30 to 80, the melting point of (B9) being lowerthan 100° C. or not observed when measured with a differential scanningcalorimeter.

In the solar cell-sealing sheet according to the ninth aspect of theinvention, soft propylene copolymer (B9) is preferablypropylene/ethylene/α-olefin copolymer (B9-1) containing 45 to 92 mol %of propylene-derived structural units, 5 to 25 mol % of ethylene-derivedstructural units, and 3 to 30 mol % of C₄-C₂₀ α-olefin-derivedstructural units, the melting point of (B9-1) being lower than 100° C.or not observed when measured with DSC.

The solar cell-sealing sheet according to the ninth aspect preferablycontains 100 parts by weight of thermoplastic resin composition (X9) and0.1 to 5 parts by weight of coupling agent (Y9).

The solar cell-sealing sheet according to the ninth aspect of theinvention is preferably non-crosslinked.

The solar cell-sealing sheet according to the ninth aspect of theinvention preferably has an internal haze of 1.0% to 10% when the sheethas a thickness of 1 mm.

The electrical/electronics element-sealing sheet according to the tenthaspect of the invention has layer (I-10) made of an ethylene-basedcopolymer having a Shore A hardness of 50 to 90 and an ethylene contentof 60 to 95 mol %; and layer (II-10) made of thermoplastic resincomposition (X10) containing 0 to 90 parts by weight of propylene-basedpolymer (A10) whose melting point is 100° C. or higher as measured witha differential scanning calorimeter and 10 to 100 parts by weight ofpropylene-based copolymer (B10), wherein the total of (A10) and (B10) is100 parts by weight. Here, copolymer (B10) is a copolymer of propyleneand at least one olefin selected from ethylene and C₄-C₂₀ α-olefins andhas a Shore A hardness of 30 to 80 and the melting point of (B10) islower than 100° C. or not observed when measured with a differentialscanning calorimeter.

In the electrical/electronics element-sealing sheet according to thetenth aspect of the invention, layer (I-10) preferably further contains0.1 to 5 parts by weight of a silane coupling agent, 0 to 5 parts byweight of an organic peroxide, and 0 to 5 parts by weight of aweathering stabilizer relative to 100 parts by weight of theethylene-based copolymer.

In the electrical/electronics element-sealing sheet according to thetenth aspect of the invention, the ethylene-based copolymer ispreferably a copolymer obtained using ethylene and at least one monomerselected from the group consisting of vinyl acetate, acrylic esters,methacrylic esters, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene,and 1-octene.

In the electrical/electronics element-sealing sheet according to thetenth aspect of the invention, thermoplastic resin composition (X10)preferably has a permanent compression set measured at 23° C. of 5% to35% and a permanent compression set measured at 70° C. of 50% to 70%.

In the electrical/electronics element-sealing sheet according to thetenth aspect of the invention, layer (I-10) made of the ethylene-basedcopolymer and layer (II-10) made of thermoplastic resin composition(X10) are preferably directly laminated with each other.

The solar cell-sealing sheet of the tenth aspect of the inventioncomprises the above electrical/electronics element-sealing sheet.

The solar cell module of the tenth aspect of the invention is fabricatedwith the above solar cell-sealing sheet.

Preferably, the solar cell module of the tenth aspect of the inventionfurther has a layer made of glass or polyester resin, wherein the solarcell-sealing sheet is bonded to the layer made of glass or polyesterresin via layer (I-10).

Furthermore, the solar cell module of the tenth aspect of the inventionpreferably has a silicon solar cell element, wherein the solarcell-sealing sheet is bonded to the silicon solar cell element via layer(II-10).

The electric power generator of the tenth aspect of the invention hasthe above solar cell module.

Effects of the Invention

The present invention provides propylene-based resin compositionssuitable for various applications and the use thereof.

The thermoplastic resin composition of the first aspect of the inventionis excellent in mechanical properties and also in rubber elasticity andpermanent compression set at high temperatures as well as normaltemperature. When it contains a softener, the composition has excellentbalance, especially at high temperatures, between appearance-retainingability and rubber elasticity and permanent compression set. The moldedarticle of the first aspect of the invention exhibits excellentmechanical properties and also excellent rubber elasticity and permanentcompression set at high temperatures as well as normal temperaturebecause the article contains at least one portion made of the abovethermoplastic resin composition. In addition, when a softener iscontained, the molded article has excellent balance, especially at hightemperature, between the appearance-retaining ability and the rubberelasticity and permanent compression set. The thermoplastic resincomposition of the first aspect is suitably used for variousapplications owing to the above properties.

The molded article made of the thermoplastic resin composition of thesecond aspect of the invention or the crosslinked material thereofexhibits well-balanced flexibility and scratch resistance and also hasexcellent whitening resistance. The article, therefore, exerts excellentperformances as various molded articles such as automobile interior andexterior components, home electric appliance components, constructionand building components, wrapping sheets, cap liners, gaskets, andconvenience goods.

The propylene-based polymer composition according to the third aspect ofthe invention provides molded articles that are particularly excellentin mechanical properties, transparency, whitening (on orientation andheat treatment), and also are excellent in impact resistance, scratchresistance, flexibility, transparency, stretching property, rubberelasticity at room and high temperatures. Molded articles made of theabove composition are excellent in impact resistance, scratchresistance, flexibility, transparency, stretching property,room-temperature rubber elasticity, and high-temperature rubberelasticity.

The film of the fourth aspect of the invention is excellent intransparency, flexibility, stretching property, impact resistance, andorientation property (low-temperature orientation property), especiallyexcellent in shrinking properties (high heat shrink ratio and reducedspontaneous shrink at room temperature). The film of the fourth aspectprovides a high-performance heat-shrinkable film. The resin compositionof the fourth aspect of the invention provides films and heat-shrinkablefilms excellent in transparency, flexibility, stretching property,impact resistance, drawing property (low-temperature drawing property),and especially shrinking properties.

The polyolefin decorative sheet of the fifth aspect of the invention isexcellent in flexibility, scratch resistance, abrasion resistance,whitening resistance on stretching, whitening resistance on folding,wrinkle resistance, heat resistance, water resistance, compression setresistance, and mechanical strength (strength at break). In addition,the sheet can avoid problems such as dioxin generation on incinerationand adverse effects of plasticizers on human bodies.

The propylene-based resin composition of the sixth aspect of theinvention contains a large amount of an inorganic filler and isexcellent in flexibility, mechanical strength, elongation at break, andscratch resistance. When it contains oil, the propylene-based resincomposition of the sixth aspect of the invention is especially excellentin scratch resistance and low-temperature embrittlement resistance.Further, when it contains a graft-modified polymer, the propylene-basedresin composition of the sixth aspect of the invention is especiallyexcellent in scratch resistance. The method for producingpropylene-based resin compositions according to the sixth aspect of theinvention provides propylene-based resin compositions excellent inflexibility, mechanical strength, elongation at break, flame retardance,and especially in scratch resistance. The propylene-based polymercomposition of the sixth aspect of the invention is suitable for use inproducing the above propylene-based resin composition, and inparticular, provides the composition with excellent scratch resistance.The propylene-based resin composition of the sixth aspect of theinvention is also suitable for use in molded articles excellent in flameretardance, especially for electrical wires, etc. because of the highcontent of inorganic filler.

The material for foam of the seventh aspect of the invention providesfoams with a low specific gravity and a small permanent compression setexcellent in tear strength, low resilience, and scratch resistance. Thefoam of the seventh aspect of the invention has a low specific gravity,a small permanent compression set, and is excellent in tear strength,low resilience, and scratch resistance. The foam of the seventh aspectof the invention may be used in a laminate. The foam and laminate of theseventh aspect of the invention have a low specific gravity, a smallpermanent compression set, and is excellent in tear strength, lowresilience, and scratch resistance; therefore they are suitable for usein footwear and footwear components.

The resin composition of the eighth aspect of the invention is wellheat-bonded to inorganic materials such as metal and glass and tovarious plastic materials and also excellent in peel strength over awide range of temperature. Further, a laminate obtained from the resincomposition of the eighth aspect of the invention is excellent inflexibility, heat resistance, transparency, scratch resistance, rubberelasticity, and mechanical strength; therefore it can be used suitablyfor various applications.

The solar cell-sealing sheet of the ninth aspect of the invention causesno adverse effect on the solar cell elements because it does notgenerate gas derived from decomposition of the component materials. Thesheet is excellent in heat resistance, mechanical strength, flexibility(solar cell-sealing property), and transparency. In addition, becausecrosslinking of the component materials is not necessary, the time forsheet molding and time for solar cell module production can besignificantly shortened, and also used solar cells can be easilyrecycled.

The tenth aspect provides an electrical/electronic element-sealing sheetwith excellent adhesion to glass and others. The electrical/electronicelement-sealing sheet is suitably used outdoors and practically valuablein sealing of solar cell elements and other uses.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A shows the intensity of magnetization in decay process for thesample prepared in Example 3-1.

FIG. 1B shows the intensity of magnetization in decay process for thesample prepared in Example 3-2.

FIG. 1C shows the intensity of magnetization in decay process for thesample prepared in Comparative Example 3-1.

FIG. 1D shows the intensity of magnetization in decay process for thesample prepared in Comparative Example 3-2.

FIG. 1E shows the intensity of magnetization in decay process for thesample prepared in Comparative Example 3-3.

FIG. 2A shows an example of a decorative board using the polyolefindecorative sheet of the fifth aspect, in which the decorative board hasa layer made of propylene-based polymer composition (X5).

FIG. 2B shows an example of a decorative board using the polyolefindecorative sheet of the fifth aspect, in which the decorative board hasa laminate composed of a layer made of propylene-based polymercomposition (X5) and a layer made of a polyolefin-based resincomposition other than propylene-based polymer composition (X5).

FIG. 3 shows an exemplary embodiment in which a solar cell-sealing sheetis applied.

FIG. 4 is a cross-sectional view illustrating schematically the solarcell module structure of an preferred embodiment related to the tenthaspect; the solar cell module is sealed between 32 and 42, that is,between layers (II-10).

EXPLANATIONS OF SYMBOLS

-   -   1: Solar cell module-protecting sheet (front protective sheet)    -   2: Solar cell module-protecting sheet (back protective sheet)    -   3: Solar cell-sealing sheet    -   4: Solar cell-sealing sheet    -   31: Layer (I-10)    -   41: Layer (I-10)    -   32: Layer (II-10)    -   42: Layer (II-10)    -   5: Solar cell element

BEST MODE FOR CARRYING OUT THE INVENTION 1. First Aspect

Hereinafter, the first aspect of the present invention is explained indetail.

<Isotactic Polypropylene (A1)>

Isotactic polypropylene (A1) used in the first aspect of the inventionis a polypropylene whose isotactic pentad fraction determined by NMR is0.9 or more, and preferably 0.95 or more.

The isotactic pentad fraction (mmmm) is measured and determined by themethod described in a prior publication (Japanese Patent Laid-OpenPublication No. 2003-147135).

Isotactic polypropylenes (A1) include homopolypropylene and copolymersof propylene and at least one C₂-C₂₀ α-olefin except propylene. TheC₂-C₂₀ α-olefins except propylene include ethylene, 1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Of these,ethylene or C₄-C₁₀ α-olefins are preferable.

These α-olefins may form a random or block copolymer with propylene.

The α-olefin-derived structural units may be present in thepolypropylene in a ratio of 35 mol % or less, and preferably 30 mol % orless.

Isotactic polypropylene (A1) preferably has a melt flow rate (MFR) at230° C. under a load of 2.16 kg determined in accordance with ASTM D1238in the range of 0.01 to 1000 g/10 min, and preferably 0.05 to 100 g/10min.

There may be used, if necessary, a plurality of isotactic polypropylenes(A1) in combination, for example, two or more components different inmelting point or rigidity.

As isotactic polypropylene (A1), there may be used, according to desiredproperties, anyone or combination selected from homopolypropyleneexcellent in heat resistance (known homopolypropylene, generally having3 mol % or less of copolymerized components except propylene), blockpolypropylene having well-balanced heat resistance and flexibility(known block polypropylene, generally containing 3 to 30 wt % ofn-decane-soluble rubber components), and random polypropylene havingwell-balanced flexibility and transparency (known random polypropylene,typical melting point is 110° C. to 150° C. as measured with a DSC).

Such isotactic polypropylene (A1) can be produced, for example, bypolymerizing propylene or copolymerizing propylene and the α-olefin(s),with a Ziegler catalyst system composed of a solid catalyst componentcontaining magnesium, titanium, halogen, and an electron donor asessential components, an organoaluminum compound, and an electron donor,or a metallocene catalyst system containing a metallocene as onecatalytic component.

<Propylene/Ethylene/α-Olefin Copolymer (B1)>

Propylene/ethylene/α-olefin random copolymer (B1) used in the firstaspect contains propylene-derived structural units in an amount of 45 to89 mol %, preferably 52 to 85 mol %, and more preferably 60 to 80 mol %,ethylene-derived structural units in an amount of 10 to 25 mol %,preferably 10 to 23 mol %, and more preferably 12 to 23 mol %, andoptionally C₄-C₂₀ α-olefin-derived structural units (a1) in an amount of0 to 30 mol %, preferably 0 to 25 mol %, and more preferably 0 to 20 mol%. When C₄-C₂₀ α-olefin-derived structural units (a1) are contained asan essential component, the content of propylene-derived structuralunits is preferably 45 to 89 mol %, more preferably 52 to 85 mol %, andstill more preferably 60 to 80 mol %; the content of ethylene-derivedstructural units is preferably 10 to 25 mol %, more preferably 10 to 23mol %, and still more preferably 12 to 23 mol %; and the content of theC₄-C₂₀ α-olefin-derived structural units (a1) is preferably 1 to 30 mol%, more preferably 3 to 25 mol %, and still more preferably 5 to 20 mol%.

Propylene/ethylene/α-olefin copolymer (B1) containing propylene-derivedstructural units, ethylene-derived structural units, and optional C₄-C₂₀α-olefin-derived structural units in the above ratio has goodcompatibility with isotactic polypropylene (A1), and the resultantpropylene-based polymer composition is likely to be sufficient intransparency, flexibility, heat resistance, and scratch resistance.

The desirable intrinsic viscosity [η] of propylene/ethylene/α-olefincopolymer (B1) is generally 0.01 to 10 dl/g and preferably 0.05 to 10dl/g when measured in decalin at 135° C. With the above range ofintrinsic viscosity [η], propylene/ethylene/α-olefin random copolymer(B1) is excellent in weatherability, ozone resistance, resistance tothermal aging, low-temperature characteristics, resistance to dynamicfatigue, and others.

The stress at 100% elongation (M100) of propylene/ethylene/α-olefincopolymer (B1) is generally 4 MPa or less, preferably 3 MPa or less, andmore preferably 2 MPa or less, when measured in accordance with JISK6301 with a JIS #3 dumbbell at span of 30 mm at a tensile speed of 30mm/min at 23° C. With the above range of stress at 100% elongation,propylene/ethylene/α-olefin copolymer (B1) exhibits excellentflexibility, transparency, and rubber elasticity.

The crystallinity of propylene/ethylene/α-olefin copolymer (B1)determined by X-ray diffractometry is generally 20% or less, andpreferably 0 to 15%.

It is desired that propylene/ethylene/α-olefin copolymer (B1) has asingle glass transition temperature (Tg) and the Tg measured with a DSCis generally −10° C. or lower, and preferably −15° C. or lower. With theabove range of Tg, propylene/ethylene/α-olefin copolymer (B1) exhibitsexcellent cold-temperature resistance and low-temperaturecharacteristics.

When propylene/ethylene/α-olefin copolymer (B1) exhibits a melting point(Tm in ° C.) in the endothermic curve obtained with a DSC, generally itsmelting endothermic entalpy, ΔH, is 30 J/g or less and the followingrelation is satisfied between C₃ (propylene) content (mol %) and ΔH(J/g) wherein “C₃ content” means the proportion of propylene-derivedstructural units determined by analyzing the C¹³-NMR spectrum.

ΔH<345 Ln (C₃ content in mol %)-1492,

wherein, 76≦C₃ content (mol %)≦90.

In order to obtain propylene/ethylene/α-olefin copolymer (B1) satisfyingthe above relation between propylene content (mol %) and meltingendothermic enthalpy ΔH (J/g), the crystallinity of the copolymer islowered by appropriately selecting polymerization conditions. Forexample, the copolymer with a low crystallinity can be obtained byselecting an appropriate catalyst. In propylene/ethylene/α-olefincopolymer (B1) obtained with such a catalyst, even when the propylenecontent is unchanged, the melting endothermic entalpy AH decreases,thereby satisfying the above relation between propylene content (mol %)and ΔH (J/g). An example of suitable catalysts for lowering thecrystallinity is disclosed in Examples of the present specification.

The crystallinity of propylene/ethylene/α-olefin copolymer (B1) can beregulated also by selecting the polymerization temperature and pressureas appropriate. For example, elevating the polymerization temperaturecan yield the copolymer with a lower crystallinity. Reducing thepolymerization pressure also yields the copolymer with a lowercrystallinity. Such polymerization conditions result inpropylene/ethylene/α-olefin copolymer (B1) with a lower meltingendothermic entalpy, ΔH, thereby satisfying the above relation betweenpropylene content (mol %) and ΔH (J/g), even with the propylene contentunchanged.

The molecular weight distribution (Mw/Mn, relative to polystyrenestandards, Mw: weight-average molecular weight, Mn: number-averagemolecular weight) measured by gel permeation chromatography (GPC) ispreferably 4.0 or less, more preferably 3.0 or less, and still morepreferably 2.5 or less.

The melting point of propylene/ethylene/α-olefin copolymer (B1) isgenerally lower than 100° C., or preferably not observed when measuredwith a DSC. Here, “melting point is not observed” means that any crystalmelting peak having a heat of crystal melting of 1 J/g or more is notobserved in the temperature range of −150° C. to 200° C. The measurementconditions are as described in Examples of the first aspect ofinvention.

The triad tacticity (mm-fraction) of propylene/ethylene/α-olefincopolymer (B1) determined by ¹³C-NMR is preferably 85% or more, morepreferably 85% to 97.5%, still more preferably 87% to 97%, andparticularly preferably 90% to 97%. With the above range of mm-fraction,the copolymer is particularly excellent in balance of flexibility andmechanical strength, and therefore suitable for the first aspect of theinvention. The mm-fraction can be determined by the method described inWO 04/087775 from Page 21 line 7 to Page 26 line 6.

Propylene/ethylene/α-olefin copolymer (B1) may be partly graft-modifiedwith a polar monomer. The polar monomers include hydroxylgroup-containing ethylenically unsaturated compounds, aminogroup-containing ethylenically unsaturated compounds, epoxygroup-containing ethylenically unsaturated compounds, aromatic vinylcompounds, unsaturated carboxylic acids and derivatives thereof, vinylesters, vinyl chloride, and others.

Such modified propylene/ethylene/α-olefin copolymer is obtained bygraft-polymerizing the polar monomer to propylene/ethylene/α-olefincopolymer (B1). In graft polymerization of propylene/ethylene/α-olefincopolymer (B1) with the polar monomer, the polar monomer is used in anamount of generally 1 to 100 parts by weight, and preferably 5 to 80parts by weight, relative to 100 parts by weight ofpropylene/ethylene/α-olefin copolymer (B1). A radical initiator isgenerally used in the graft polymerization.

As the radical initiator, an organic peroxide, an azo compound, orothers may be used. The radical initiator may be mixed directly withpropylene/ethylene/α-olefin copolymer (B1) and the polar monomer, or maybe dissolved in a small amount of an organic solvent prior to mixing.Any organic solvent capable of dissolving the radical initiator may beused without particular limitations.

A reducing substance may be used in graft polymerization of the polarmonomer to propylene/ethylene/α-olefin copolymer (B1). The reducingsubstance increases the grafting amount of the polar monomer.

Conventional methods may be used for graft-modification ofpropylene/ethylene/α-olefin copolymer (B1) with the polar monomer. Forexample, there may be mentioned a method in whichpropylene/ethylene/α-olefin copolymer (B1) is dissolved in an organicsolvent; the polar monomer, radical initiator, and others are added tothe resulting solution; and the reaction is conducted at 70 to 200° C.,preferably 80 to 190° C., for 0.5 to 15 hr, preferably 1 to 10 hr.

Alternatively, the modified propylene/ethylene/α-olefin copolymer can beproduced by reacting propylene/ethylene/α-olefin copolymer (B1) with thepolar monomer using an extruder or others without any solvent. It isdesirable that the reaction is performed generally at a temperatureequal to or higher than the melting point of propylene/ethylene/α-olefincopolymer (B1), specifically at 120 to 250° C., generally for 0.5 to 10min.

The desirable modification ratio (ratio of the polar monomer grafted) ofthe modified propylene/ethylene/α-olefin copolymer is generally 0.1 to50 wt %, preferably 0.2 to 30 wt %, and more preferably 0.2 to 10 wt %.

When the propylene-based polymer composition of the first aspect of theinvention contains the modified propylene/ethylene/α-olefin copolymer,it attains excellent adhesion and compatibility with other resins, andmolded articles formed from the propylene-based polymer composition haveimproved surface wettability in some cases.

Propylene/ethylene/α-olefin copolymer (B1) can be produced with themetallocene catalyst used for producing isotactic polypropylene (A1) bysimilar procedures to those in producing (A1), but the production is notlimited thereto. For example, the catalyst described in WO 04/087775 maybe used.

<Styrene-Based Elastomer (C1)>

As styrene-based elastomer (C1) used in the first aspect of theinvention, styrene/diene thermoplastic elastomers can be given, but thestyrene-based elastomer is not limited thereto. In particular, blockcopolymer elastomers and random copolymer elastomers are preferred. Insuch elastomers, the styrene-type monomer is exemplified by styrene,α-methylstyrene, p-methylstyrene, vinylxylene, vinylnaphthalene,mixtures thereof, and others; and the diene-type monomer is exemplifiedby butadiene, isoprene, pentadiene, mixtures thereof, and others.

The typical examples of styrene-based elastomer (C1) includehydrogenated diene polymers comprising polybutadiene block segments andstyrene type compound (including styrene itself, the same applieshereinafter)/butadiene copolymer block segments; hydrogenated dienepolymers comprising polyisoprene block segments and styrene typecompound/isoprene copolymer block segments; block copolymers comprisingpolymer blocks mainly derived from a styrene type compound and polymerblocks mainly derived from a conjugated diene; hydrogenated product ofrandom copolymers of styrene type compound and conjugated diene; andhydrogenated derivatives of block copolymers comprising polymer blocksmainly derived from a styrene type compound and polymer blocks mainlyderived from a conjugated diene.

The content of styrene-type monomer component in the styrenethermoplastic elastomer is not particularly limited, but is preferablyin the range of 5 to 40 wt %, considering flexibility and rubberelasticity in particular.

Styrene-based elastomers (C1) may be used alone or in combination.Commercial products may also be used as styrene-based elastomer (C1).

<Ethylene/α-Olefin Random Copolymer (D1)>

Ethylene/α-olefin random copolymer (D1) optionally used in the firstaspect of the invention refers to a copolymer of ethylene and a C₃-C₂₀α-olefin, preferably a C₃-C₁₀ α-olefin. Copolymers having the followingproperties are preferably used:

(a) the density in accordance with ASTM 1505 at 23° C. is 0.850 to 0.910g/cm³, preferably 0.860 to 0.905 g/cm³, and more preferably 0.865 to0.895 g/cm³; and

(b) the MFR measured at 190° C. under a load of 2.16 kg is 0.1 to 150g/10 min, and preferably 0.3 to 100 g/10 min.

Ethylene/α-olefin random copolymer (D1) having these properties ispreferably used, because a softener is well retained in the composition.

There is no limitation on the method for producing the ethylene/α-olefinrandom copolymer (D1). The copolymer can be produced by copolymerizingethylene and the α-olefin with a radical-polymerization catalyst,Philips catalyst, Ziegler-Natta catalyst, or a metallocene catalyst. Inparticular, the copolymer produced with a metallocene catalyst has amolecular weight distribution (Mw/Mn) of generally 3 or less, which issuitable for use in the first aspect of the invention.

The crystallinity of ethylene/α-olefin random copolymer (D1) measured byX-ray diffractometry is generally 40% or less, preferably 0 to 39%, andmore preferably 0 to 35%.

Specific examples of the C₃-C₂₀ α-olefin used as a co-monomer includepropylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,1-decene, and 1-dodecene. These are used alone or in combination. Amongthem, propylene, 1-butene, 1-hexene, and 1-octene are preferable.Furthermore, if necessary, a small amount of (an)other co-monomer(s),for example, a diene such as 1,6-hexadiene or 1,8-octadiene, or acycloolefin such as cyclopentene, may be used. The α-olefin content inthe copolymer is generally 3 to 50 mol %, preferably 5 to 30 mol %, andmore preferably 5 to 25 mol %.

The molecular structure of the copolymer may be linear or branched withlong or short side-chains. Further, a plurality of differentethylene/α-olefin random copolymers (D1) may be used as a mixture.

Ethylene/α-olefin random copolymer (D1) can be produced by known methodsusing a vanadium catalyst, a titanium catalyst, a metallocene catalyst,or the like. For example, there may be mentioned the method described inJapanese Patent Laid-Open Publication No. H10-212382.

<Softener (E1)>

Softener (E1) optionally used in the first aspect of the invention maybe selected from various oils such as paraffin oil and silicon oil. Inparticular, paraffin oil is suitably used. For the oils suitably used,the kinematic viscosity at 40° C. is 20 to 800 cSt (centistokes) andpreferably 40 to 600 cSt, the pour point is 0 to −40° C. and preferably0 to −30° C., and the flash point (COC test) is 200 to 400° C. andpreferably 250 to 350° C.

One of the oils suitably used for the first aspect of the invention isnaphthene process oil, which is a petroleum-derived softener blended inrubber processing for softening, dispersing components, lubricating, orother purposes. This oil contains 30 to 45 wt % of naphthene-typehydrocarbons. Blending such process oil further improves the melt-pourpoint of resin compositions on molding and the flexibility of moldedarticles, and also reduces occurrence of surface stickiness caused bybleeding in molded articles. In the first aspect, a naphthene processoil having an aromatic hydrocarbon content of 10 wt % or less is used.Using the naphthene oil reduces incidence of surface bleeding in moldedarticles.

<Thermoplastic Resin Composition (X1)>

Thermoplastic resin composition (X1) of the first aspect of theinvention contains (A1), (B1), (C1), and if necessary, (D1):

1 to 90 wt % of isotactic polypropylene (A1);

9 to 98 wt % of propylene/ethylene/α-olefin copolymer (B1) containing 45to 89 mol % of propylene-derived structural units, 10 to 25 mol % ofethylene-derived structural units, and if necessary, 0 to 30 mol % ofC₄-C₂₀ α-olefin-derived structural units (a1);

1 to 80 wt % of styrene-based elastomer (C1); and

0 to 70 wt % of ethylene/α-olefin copolymer (D1) having a density of0.850 to 0.910 g/cm³, wherein the total of (A1)+(B1)+(C1)+(D1) is 100 wt%.

The content of component (A1) is preferably 5 to 80 wt %, and morepreferably 10 to 75 wt %; the content of component (B1) is preferably 5to 92 wt %, and more preferably 10 to 75 wt %; the content of component(C1) is preferably 3 to 75 wt %, and more preferably 5 to 65 wt %; andthe content of component (D1) is preferably 0 to 65 wt %, and morepreferably 0 to 60 wt %.

When component (D1) is contained as an essential component, the contentof each component is as follows: the content of component (A1) ispreferably 1 to 89 wt %, more preferably 5 to 80 wt %, and still morepreferably 10 to 75 wt %; the content of component (B1) is preferably 9to 97 wt %, more preferably 5 to 90 wt %, and still more preferably 10to 75 wt %; the content of component (C1) is preferably 1 to 80 wt %,more preferably 3 to 75 wt %, and still more preferably 5 to 65 wt %;and the content of component (D1) is preferably 1 to 70 wt %, morepreferably 2 to 65 wt %, and still more preferably 5 to 60 wt %.

Thermoplastic resin composition (X1) preferably contains softener (E1)in an amount of 1 to 400 parts by weight, preferably 1 to 200 parts byweight, and still more preferably 1 to 150 parts by weight, relative to100 parts by weight of the total of components (A1), (B1), (C1), and ifany, (D1).

As long as the objective of the first aspect of the invention is notimpaired, thermoplastic resin composition (X1) may also contain otherresins, other rubbers, inorganic filler, or others; and also may containadditives such as weathering stabilizers, heat stabilizers, antistaticagents, anti-slip agents, anti-blocking agents, anti-fogging agents,lubricants, pigments, dyes, plasticizers, anti-aging agents,hydrochloric acid absorbers, antioxidants, and nucleating agents. Theamount of these additional resins, rubbers, inorganic filler, andadditives to be mixed in thermoplastic resin composition (X1) is notparticularly limited unless the objective of the first aspect isimpaired. In an embodiment, the total of isotactic polypropylene (A1),propylene/ethylene/α-olefin random copolymer (B1), styrene-basedelastomer (C1), if necessary ethylene/α-olefin random copolymer (D1),and if necessary softener (E1) is 60 to 100 wt % and preferably 80 to100 wt % of the whole composition, and the remainder is accounted for bythe above-described other resins, rubbers, additives, inorganic filler,and others.

Thermoplastic resin composition (X1) can be obtained with a knownkneader (for example, single-screw or twin-screw extruder, Banburymixer, roll mixer, calendar mixer, etc.), preferably with a moldingmachine capable of continuous kneading and extruding such as asingle-screw or twin-screw extruder.

Although the composition is preferably non-crosslinked for facilitatingrecycling in accordance with the objective of the first aspect of theinvention, it may be crosslinked as necessary. For crosslinking, theremay be employed a method of dynamic crosslinking using a knowncrosslinker or crosslinking auxiliary or a method in which thermoplasticresin composition (X1) is kneaded with a crosslinker, crosslinkingauxiliary, or others and molded, followed by post-crosslinking withheating or electron beam irradiation.

<Molded Article at Least Part of which is Made of Thermoplastic ResinComposition (X1)>

Thermoplastic resin composition (X1) according to the first aspect ofthe invention may be shaped into various articles, for example, sheets,unoriented or oriented films, filaments, and others with various shapes.The molded article at least part of which is made of thermoplastic resincomposition (X1) may be a molded article the whole of which is made ofthermoplastic resin composition (X1) or may be a composite article ofthe thermoplastic resin composition with other materials in which aportion of the article is made of thermoplastic resin composition (X1).For example, the molded article according to the first aspect of theinvention may be a multilayer laminate. In this case, at least one layerof the laminate contains thermoplastic resin composition (X1). Forexample, there may be mentioned multilayer films, multilayer sheets,multilayer containers, multilayer tubes, multilayer coating films inwhich the composition is contained as one of the constituents ofwater-based paint, and others.

The molded articles include, specifically, molded articles obtained byknown heat molding such as extrusion molding, injection molding,inflation molding, blow molding, extrusion blow molding, injection blowmolding, press molding, vacuum molding, calendar molding, and foammolding. Hereinafter, the molded article will be explained withreference to several examples.

For example, when the molded article according to the first aspect ofthe invention is an extrusion-molded article, the shapes and producttypes are not particularly limited, and include sheets, films(unoriented), pipes, hoses, electrical wire covers, tubes, and others.In particular, preferred are sheets (for example, skin material, etc.),films, tubes, catheters, monofilaments, nonwoven fabrics, and others.

For extrusion molding of thermoplastic resin composition (X1), knownextruders and molding conditions can be employed. For example, a moldedarticle with a desired shape can be obtained by extruding meltedthermoplastic resin composition (X1) with an extruder, such assingle-screw extruder, kneading extruder, ram extruder, or gearextruder, through a predetermined die or the like.

An oriented film can be obtained by drawing the above extruded sheets orfilms (unoriented) by known methods such as tentering(longitudinal-transverse or transverse-longitudinal orientation),simultaneous biaxial orientation, and uniaxial orientation.

In drawing the sheet or unoriented film, the draw ratio is generallyabout 20 to 70 in biaxial drawing, and about 2 to 10 in uniaxialdrawing. It is preferred that the oriented film obtained by drawing hasa thickness of about 5 to 200 μm.

As film-shape molded articles, inflation films may be produced. Oninflation molding, drawdown is not likely to develop.

Such sheet-shaped or film-shaped molded articles at least part of whichis made of thermoplastic resin composition (X1) as described above areless electrostatically charged and are excellent in rigidity such astensile modulus, heat resistance, stretching property, impactresistance, aging resistance, transparency, translucency, gloss,stiffiness, moisture resistance, and gas barrier property. They can bewidely used as packaging films and others. The sheet-shaped orfilm-shaped molded article made of thermoplastic resin composition (X1)may be a multilayer molded article having at least one layer ofthermoplastic resin composition (X1).

Filament-shaped molded articles can be produced, for example, byextruding melted thermoplastic resin composition (X1) through aspinneret. The filament thus obtained may be further drawn. The drawingshould be performed to orient the molecules along at least one axis ofthe filament, and the draw ratio is preferably about 5 to 10. Thefilament made of thermoplastic resin composition (X1) is lesselectrostatically charged and is excellent in transparency, rigidity,heat resistance, impact resistance, and stretching property. As themethod for producing nonwoven fabrics, there may be mentioned thespunbond method and the melt-blowing method. The resulting nonwovenfabrics are less electrostatically charged and are excellent inrigidity, heat resistance, impact resistance, and stretching property.

Injection-molded articles can be produced by injection moldingthermoplastic resin composition (X1) into various shapes using knowninjection molding machines and conditions. The injection-molded articlesmade of thermoplastic resin composition (X1) are less electrostaticallycharged and are excellent in transparency, rigidity, heat resistance,impact resistance, surface gloss, chemical resistance, abrasionresistance, and the like; hence they are widely used in automobileinterior trims, automobile exterior components, housings for homeelectric appliances, containers, and others.

Blow-molded articles can be produced by blow molding thermoplastic resincomposition (X1) using known blow molding machines and conditions. Here,the blow-molded article at least part of which is made of thermoplasticresin composition (X1) may be a multilayer molded article containing atleast one layer of thermoplastic resin composition (X1).

For example, in extrusion blow molding, a hollow molded article can beproduced by extruding thermoplastic resin composition (X1) through a diein a molten state at a resin temperature of 100° C. to 300° C. to form atubular parison, which is held in a mold with a desired shape andsubsequently shaped to the mold at a resin temperature of 130° C. to300° C. by blowing air thereinto. The blow ratio is desirably about 1.5to 5 in the transverse direction.

In injection blow molding, a hollow molded article can be produced byinjecting thermoplastic resin composition (X1) into a parison mold at aresin temperature of 100° C. to 300° C. to form a parison, which is heldin a mold with a desired shape and subsequently shaped to the mold at aresin temperature of 120° C. to 300° C. by blowing air thereinto. Theblow ratio is desirably 1.1 to 1.8 in the longitudinal direction and 1.3to 2.5 in the transverse direction.

The blow-molded article at least part of which is made of thermoplasticresin composition (X1) is excellent in transparency, flexibility, heatresistance, impact resistance, and moisture resistance.

The press-molded articles include stamping-molded articles. For example,when abase material and a skin material are press-molded at a time intoa composite (stamping molding), the base material can be formed from thepropylene composition according to the first aspect of the invention.

Such stamping-molded articles include, specifically, automobile interiorcomponents such as door trims, rear package trims, sheet back garnishes,and instrumental panels.

The press-molded articles at least part of which is made ofthermoplastic resin composition (X1) are less electrostatically chargedand are excellent inflexibility, heat resistance, transparency, impactresistance, aging resistance, surface gloss, chemical resistance, andabrasion resistance.

In one embodiment of the first aspect of the invention, the moldedarticle having at least portion made of the thermoplastic resincomposition (X1) is a film or sheet, a monofilament, a fiber, ornonwoven fabric. These are useful as stretching materials.

The molded articles at least part of which is made of the thermoplasticresin composition (X1) are excellent in mechanical properties such ashardness, excellent in rubber elasticity and permanent compression setnot only at normal temperature but also at high temperatures, andexcellent in transparency and scratch resistance. In addition, even whenthe softener is contained, the articles are well-balanced inappearance-retaining ability and rubber elasticity and permanentcompression set, particularly at high temperature. The molded articlesare easily recycled and produced in a cost-effective manner. Therefore,thermoplastic resin composition (X1) is suitable for use for automobileinterior components, automobile exterior components, home electricappliance components, construction and building components, wrappingsheets, cap liners, gaskets, and convenience goods. In particular, thecomposition is suitably used for automobile interior and exteriorcomponents, which are required to exhibit rubber elasticity even at hightemperatures.

The automobile interior components at least part of which is made ofthermoplastic resin composition (X1) include, for example, door trims,gaskets, and others.

The automobile exterior components at least part of which is made ofthermoplastic resin composition (X1) include bumpers and others.

The home electric appliance components at least part of which is made ofthermoplastic resin composition (X1) include packings and others.

The construction or building components at least part of which is madeof thermoplastic resin composition (X1) include waterproof sheets,floorings, and others.

The packaging sheets at least part of which is made of thermoplasticresin composition (X1) include mono-layer sheets and multilayer sheetsusing the resin composition of the first aspect of the invention in atleast one layer.

The cap liners at least part of which is made of thermoplastic resincomposition (X1) include liners for potable water bottle caps andothers. As the method for producing the cap liner, there may bementioned a method of punching out a sheet prepared from thermoplasticresin composition (X1) with a sheet-forming machine.

As the method for producing caps having the cap liner of the firstaspect, there may be mentioned, for example, (1) method in which the capliner is bonded to the inside top face of a cap with an adhesive, (2)sheet punching method in which the cap liner in molten or semi-moltenstate is bonded to the inside top face of a cap, and (3) in-shellmolding method in which the source materials for the cap liner of thefirst aspect are melt-kneaded with an extruder or the like, and the meltof the resulting composition is placed on the inside top face of a capand stamped therein into a cap liner shape. The cap liner of the firstaspect of the invention can be attached to any of plastic caps and metalcaps regardless of a cap material.

The cap having the cap liner of the first aspect of the invention can beattached to packaging containers for beverages such as mineral water,tea, carbonated drinks, sports drinks, fruits drinks, and milk beverage,and food products such as grilled meat sauce, soybean sauce, sauce,mayonnaise, and ketchup.

The convenience goods at least part of which is made of thermoplasticresin composition (X1) include grips and others.

For each of the automobile interior components, automobile exteriorcomponents, home electric appliance components, construction or buildingcomponents, packaging sheets, cap liners, gaskets, and convenience goodsat least part of which is made of thermoplastic resin composition (X1),the whole body may be made of thermoplastic resin composition (X1) or itmay be a composite of the thermoplastic resin composition with othermaterials in which a portion of the composite is made of thermoplasticresin composition (X1).

The decorative sheet at least part of which is made of thermoplasticresin composition (X1) has at least one layer made of thermoplasticresin composition (X1). Hereinafter, the decorative sheet is explained.

The decorative sheet of the first aspect of the invention is used, forexample, for conventional decorative boards in which the sheet is bondedon the surface of base materials such as plywood, steel plate, aluminumplate, particle board, MDF (medium-density fiberboard), inorganic board(such as gypsum board), concrete wall, plastic board, foam, and heatinsulator, with an adhesive or by another method. The decorative sheetsof the first aspect include building material protective sheets, forexample, a sheet used for the surface layer of floor, wall, ceiling, orother parts. Both decorative sheets and building material protectivesheets are used for protecting surfaces and for producing design such asprint or pictures.

A typical example of the decorative sheet of the first aspect of theinvention contains at least one layer of thermoplastic resin composition(X1). The decorative sheet may contain two or more layers ofthermoplastic resin composition (X1), in which case the two or morelayers may be composed of the same components or different componentsfrom each other.

The decorative sheet of the first aspect of the invention may contain,besides the layer(s) made of thermoplastic resin composition (X1), knowncomponent layers for decorative sheets, such as a layer displaying printand picture designs, a surface-coating layer, a luster-adjusting layer,a shielding layer (which prevents the substrate surface from being seenthrough a foreground layer, and in some cases, serves as a basematerial), and an adhesive layer bonding these layers together.

The structure of the decorative sheet according to the first aspect ofthe invention is not particularly limited. One example is a structure inwhich the decorative sheet contains a layer [a] made of thermoplasticresin composition (X1), at least one layer [b] selected from a printlayer, a picture layer, and a shielding layer, and optionally at leastone layer [c] selected from a surface-coating layer and aluster-adjusting layer.

Another example is a structure in which the decorative sheet contains ashielding layer [d], a layer [a] made of thermoplastic resin composition(X1), at least one layer [b] selected from a print layer and a picturelayer, and optionally at least one layer [c] selected from asurface-coating layer and a luster-adjusting layer.

The layer made of thermoplastic resin composition (X1) is excellent inscratch resistance, abrasion resistance, whitening resistance onfolding, wrinkle resistance, heat resistance, and transparency, and istherefore suitable for use as a protective layer for protecting a printor picture layer (that is, used as a surface layer protecting a print orpicture layer; a known treatment may be applied to the layer made ofthermoplastic resin composition (X1) to provide a surface-coating layer,a luster-adjusting layer, or others thereon unless the objectives of thefirst aspect of the invention are impaired). Decorative sheets with suchstructure are particularly preferable.

Since the layer made of thermoplastic resin composition (X1) is alsoexcellent in flexibility and water resistance, it can be suitably usedas one layer in combination with a layer of other components. In thiscase, the layer made of thermoplastic resin composition (X1) can bebonded without a known adhesive or an adhesive having the same effect asthe known adhesives. Specifically, sufficient bond strength can beattained by known hot-melt bonding techniques such as heat lamination,extrusion lamination, sandwich lamination, and co-extrusion.

Therefore, the layer of thermoplastic resin composition (X1) can besuitably used for a decorative sheet in combination with layers made ofa polyolefin-based resin other than the thermoplastic resin composition(X1), that is, layers made of a polyolefin-based resin out of the scopeof thermoplastic resin composition (X1) (including known adhesivepolyolefin resin layers).

The thickness of the layer made of thermoplastic resin composition (X1)is not particularly limited, but is generally 5 to 2000 μm.

To the decorative sheet or construction material protective sheet of thefirst aspect of the invention, there may be applied known treatmentssuch as embossing, engravning, and wiping.

The decorative sheet or construction material protective sheet of thefirst aspect of the invention can be suitably used in a laminate inwhich the back surface of the layer made of thermoplastic resincomposition (X1) is bonded to a layer made of a polyolefin-based resinother than thermoplastic resin composition (X1) without an adhesive. Thepolyolefin based resin other than thermoplastic resin composition (X1)used herein may be any resin other than thermoplastic resin composition(X1). That is, any resin that is not included in thermoplastic resincomposition (X1) may be used without limitations. Specifically, suchresins include polyethylene, polypropylene, poly-α-olefin,ethylene/α-olefin copolymer, ethylene/polar vinyl monomer copolymer, amixed resin composition thereof, and others.

Beside these, the above olefin-based resin may further contain additivessuch as inorganic fillers, weathering stabilizers, heat stabilizers,antistatic agents, anti-slip agents, anti-blocking agents, anti-foggingagents, lubricants, pigments, dyes, plasticizers, anti-aging agents,hydrochloric acid absorbers, antioxidants, and nucleating agents, unlessthe objectives of the first aspect of the invention are impaired. Here,“lamination without an adhesive” means direct lamination by hot-meltbonding.

There is no particular limitation on the method for producing thedecorative sheet or building material protective sheet of the firstaspect of the invention. Known methods may be employed.

There is no particular limitation on the application of the decorativesheet or building material protective sheet of the first aspect. Thesheet can be suitably used for home electric appliances and furnituresuch as TV cabinets, stereo-speaker boxes, video recorder cabinets,various storage furniture, and united furniture; housing members such asdoors, doorframes, window sashes, crown, plinth, and opening frames;furniture members such as doors of kitchen furniture and storagefurniture; building materials such as floor material, ceiling material,and wall paper; automobile interior materials; stationery; office goods;and others.

2. Second Aspect

Hereinafter, the second aspect of the present invention will bedescribed in detail.

<Isotactic Polypropylene (A2)>

Examples of isotactic polypropylenes (A2) optionally used in the secondaspect of the invention include homopolypropylene and copolymers ofpropylene and at least one C₂-C₂₀ α-olefin except propylene. Specificexamples of the C₂-C₂₀ α-olefin except propylene include the same asthose for isotactic polypropylene (A1) used in the first aspect of theinvention. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

The polypropylene may contain structural units derived from suchα-olefin in an amount of 20 mol % or less, and preferably 15 mol % orless.

The melting point of isotactic polypropylene (A2) measured with adifferential scanning calorimeter (DSC) is generally 100 to 170° C.(except 100° C.), preferably 105 to 170° C., and more preferably 110 to165° C.

There may be used, if necessary, a plurality of isotactic polypropylenes(A2) together, for example, two or more components different in meltingpoint or rigidity.

Isotactic polypropylene (A2) preferably has the same properties as thoseof isotactic polypropylene (A1) used in the first aspect of theinvention concerning an isotactic pentad fraction (mmmm) and an MFR.

In order to attain desired properties, isotactic polypropylene (A2) maybe one or more polypropylenes selected from homopolypropylene excellentin heat resistance, block polypropylene with well-balanced heatresistance and flexibility, and random polypropylene with well-balancedflexibility and transparency, like isotactic polypropylene (A1) of thefirst aspect of the invention.

Isotactic polypropylene (A2) can be produced by the method similar tothat for producing isotactic polypropylene (A1) used in the first aspectof the invention.

<Propylene/α-Olefin Copolymer (B2)>

Propylene/α-olefin copolymers (B2) used in the second aspect includepropylene/ethylene copolymer and copolymers of propylene and at leastone C₄-C₂₀ α-olefin. The C₄-C₂₀α-olefins include 1-butene, 1-pentene,1-octene, 1-decene, and others. Copolymers of propylene and at least oneC₄-C₂₀ α-olefin are preferable and propylene/1-butene copolymer is morepreferable.

The melting point of propylene/α-olefin copolymer (B2) is generally nothigher than 100° C. or not observed when measured with a differentialscanning calorimeter (DSC). The melting point is preferably 30 to 90°C., and more preferably 40 to 85° C. Here, “melting point is notobserved” means that any melting endothermic peak of crystal with amelting endothermic entalpy of crystal of 1 J/g or more is not observedin the temperature range of −150 to 200° C. The measurement conditionsare as described in Examples of the second aspect of the invention.

In propylene/α-olefin copolymer (B2), the molecular weight distribution(Mw/Mn, relative to polystyrene standards, Mw: weight-average molecularweight, Mn: number-average molecular weight) measured by gel permeationchromatography (GPC) is preferably 1 to 3, and more preferably 1.5 to2.5.

With propylene/α-olefin copolymer (B2), it is preferred that the meltingpoint of Tm (° C.) and the co-monomer content (M in mol %) determined by¹³C-NMR satisfy the relation,

146exp(−0.022 M)≧Tm≧125exp(−0.032 M).

Any copolymer satisfying the above relation may be used in the secondaspect without particular limitation on “M”, but “M” is generally in therange of 5 to 45.

In propylene/α-olefin copolymer (B2), the melt flow rate (MFR)determined at 230° C. under a load of 2.16 kg in accordance with ASTMD1238 (in the present specification, often called “MFR” (230° C.)) isgenerally 0.1 to 40 g/10 min, and preferably 0.5 to 20 g/10 min.

Propylene/α-olefin copolymer (B2) preferably has the same triadtacticity (mm-fraction) as that of propylene/ethylene/α-olefin copolymer(B1) of the first aspect of the invention, whereby the same effect canbe obtained.

Namely, the triad tacticity (mm-fraction) of propylene/α-olefincopolymer (B2) is preferably 85% or more, more preferably 85% to 97.5%,still more preferably 87% to 97%, and particularly preferably 90% to 97%as determined by ¹³C-NMR. With the above range of triad tacticity(mm-fraction), particularly well-balanced flexibility and mechanicalstrength is attained, which is desirable for the present invention. Themm-fraction can be determined with the method described in WO 04/087775from page 21, line 7 to page 26, line 6.

Propylene/α-olefin copolymer (B2) is publicly known and can be producedby the method described in WO 04/087775. Propylene/α-olefin copolymer(B2) is preferably produced using a metallocene catalyst.

It is preferred that propylene/α-olefin copolymer (B2) be notpropylene/ethylene/C₄-C₂₀ α-olefin copolymer containing 45 to 89 mol %of propylene-derived structural units, 10 to 25 mol % ofethylene-derived structural units, and 0 to 30 mol % of C₄-C₂₀4847-7471-9018.1 α-olefin-derived structural units.

<Styrene-Based Elastomer (C2)>

Styrene-based elastomer (C2) is the same as styrene-based elastomer (C1)used in the first aspect of the invention. The type and styrene contentthereof are also the same as (C1).

<Ethylene/α-Olefin Random Copolymer (D2)>

The method for producing ethylene/α-olefin random copolymer (D2) is notparticularly limited, but there is employed a known method using avanadium catalyst, a titanium catalyst, a metallocene catalyst, or thelike. In particular, the copolymer produced using the metallocenecatalyst generally has a molecular weight distribution (Mw/Mn) of 3 orless, and is suitably used for the second aspect of the invention.

Ethylene/α-olefin random copolymer (D2) is the same as ethylene/α-olefinrandom copolymer (D1) used in the first aspect of the invention exceptfor the production method.

<Softener (E2)>

Softener (E2) is the same as softener (E1) used in the first aspect ofthe invention.

<Thermoplastic Resin Composition (X2)>

Thermoplastic resin composition (X2) of the second aspect of theinvention comprises (A2), (B2), (C2), (D2), and (E2): 5 to 95 wt % ofpropylene/α-olefin copolymer (B2) whose melting point is not higher than100° C. or not observed when measured with a differential scanningcalorimeter (DSC);

5 to 95 wt % of styrene-based elastomer (C2);

0 to 90 wt % of isotactic polypropylene (A2);

0 to 70 wt % of ethylene/α-olefin copolymer (D2) whose density is 0.850to 0.910 g/cm³;

(wherein the total of (A2)+(B2)+(C2)+(D2) is 100 wt %) and

softener (E2) in an amount of 0 to 400 parts by weight relative to 100parts by weight of the total of (A2)+(B2)+(C2)+(D2).

Here, the content of component (B2) is preferably 5 to 85 wt %, and morepreferably 10 to 75 wt %; the content of component (C2) is preferably 15to 95 wt %, and more preferably 25 to 90 wt %; the content of component(A2) is preferably 0 to 80 wt %, and more preferably 0 to 65 wt %; andthe content of component (D2) is preferably 0 to 65 wt %, and morepreferably 0 to 60 wt %.

When component (A2) is contained as an essential component, the contentof component (B2) is 5 to 94 wt %, preferably 5 to 83 wt %, and morepreferably 10 to 72 wt %; the content of component (C2) is 5 to 95 wt %,preferably 15 to 95 wt %, and more preferably 25 to 90 wt %; the contentof component (A2) is 1 to 90 wt %, preferably 2 to 80 wt %, and morepreferably 3 to 65 wt %; and the content of component (D2) is 0 to 70 wt%, preferably 0 to 65 wt %, and more preferably 0 to 60 wt %.

Thermoplastic resin composition (X2) may also contain softener (E2) inan amount of 0 to 400 parts by weight, preferably 0 to 200 parts byweight, and more preferably 0 to 150 parts by weight, relative to 100parts by weight of the total of (A2), (B2), (C2), and (D2). Whencomponent (E2) is contained in the composition, the lower limit of thecontent of (E2) is not limited to, but, for example, 1 part by weight ormore relative to 100 parts by weight of the total of (A2), (B2), (C2),and (D2).

For instance, when the composition (X2) contains isotactic polypropylene(A2) as an essential component and is used for convenience goods, skinmaterials (artificial leather), cap liners, automobile interiormaterials, packing, gaskets, waterproof sheets, or the like as describedlater, the content of component (B2) is 5 to 50 wt %, preferably 15 to50 wt %, and more preferably 20 to 45 wt %; the content of component(C2) is 5 to 90 wt %, preferably 10 to 80 wt %, and more preferably 20to 75 wt %; the content of component (A2) is 5 to 45 wt %, preferably 5to 40 wt %, and more preferably 5 to 35 wt %; and the content ofcomponent (D2) is 0 to 50 wt %, preferably 0 to 40 wt %, and morepreferably 0 to 30 wt %. Here, (X2) may also contain, as an optionalcomponent, softener (E2) in an amount of 1 to 400 parts by weight,preferably 1 to 350 parts by weight, and more preferably 1 to 300 partsby weight, relative to 100 parts by weight of the total of (A2), (B2),(C2), and (D2). The composition provides well-balanced flexibility withscratch and whitening resistances, and it can be well kneaded even atlow temperatures.

For instance, when (X2) contains isotactic polypropylene (A2) as anessential component and it is used for home electric appliancecomponents, automobile exterior materials, packaging sheets,monofilaments, or the like as described later, the content of component(B2) is 5 to 45 wt %, preferably 5 to 35 wt %, and more preferably 5 to30 wt %; the content of component (C2) is 5 to 45 wt %, preferably 5 to35 wt %, and more preferably 5 to 30 wt %; the content of component (A2)is 50 to 90 wt %, preferably 60 to 90 wt %, and more preferably 65 to 90wt %; and the content of component (D2) is 0 to 30 wt %, preferably 0 to25 wt %, and more preferably 0 to 20 wt %. Here, (X2) may also contain,as an optional component, softener (E2) in an amount of 1 to 100 partsby weight, preferably 1 to 70 parts by weight, and more preferably 1 to50 parts by weight, relative to 100 parts by weight of the total of(A2), (B2), (C2), and (D2). With such composition, particularly,well-balanced mechanical properties such as tensile modulus,transparency, impact resistance, scratch resistance, and whiteningresistance can be attained.

Unless the objects of the second aspect of the invention are impaired,thermoplastic resin composition (X2) may contain other resins, otherrubbers, inorganic fillers or others; and may further contain additiveslike those for the first aspect of the invention. The content of theseadditional resins, rubbers, inorganic fillers, and additives is notparticularly limited unless the objects of the second aspect of theinvention are impaired. An exemplary embodiment concerning the contentof these additional resins, rubbers, inorganic fillers, and additives isthe same as that in the first aspect of the invention.

That is, unless the objects of the second aspect of the invention areimpaired, thermoplastic resin composition (X2) may additionally containother resins, other rubbers, inorganic fillers, or others, and alsoadditives such as weathering stabilizers, heat stabilizers, antistaticagents, anti-slip agents, anti-blocking agents, anti-fogging agents,lubricants, pigments, dyes, plasticizers, anti-aging agents,hydrochloric acid absorbers, antioxidants, and nucleating agents. Thereare no particular limitations on the amount of these additional resins,rubbers, inorganic filler, additives, and others added to thermoplasticresin composition (X2), unless the objects of the second aspect areimpaired. In an exemplary embodiment, the total of propylene/α-olefincopolymer (B2), styrene-based elastomer (C2), if necessary isotacticpolypropylene (A2), if necessary ethylene/α-olefin copolymer (D2), andif necessary softener (E2), is 60 to 100 wt %, preferably 80 to 100 wt %of the whole composition, and the remainder is accounted for by theabove-described other resins, rubbers, additives, inorganic filler, andothers.

Thermoplastic resin composition (X2) is produced with a publicly knownkneader as in the case of first aspect of the invention. Preferablemethods are also the same.

Thermoplastic resin composition (X2) may be crosslinked, if necessary.The crosslinked product of the present invention can be produced bydynamic crosslinking with a known crosslinker or crosslinking auxiliary.Alternatively, post-crosslinking may be applied by heat or irradiationwith electron beam or others to a molded article formed fromthermoplastic resin composition (X2) alone or a mixture prepared bykneading thermoplastic resin composition (X2), a crosslinker, acrosslinking auxiliary, and others.

Particularly in dynamic crosslinking, since propylene/α-olefin copolymer(B2) has a low melting point and can be molded at low temperatures,there is an advantage that thermoplastic resin composition (X2) can bedynamically crosslinked under wide range of conditions.

<Molded Article Made of Thermoplastic Resin Composition (X2) orCrosslinked Material Thereof>

Thermoplastic resin composition (X2) and crosslinked product thereof canbe used for molded articles, for example, sheets, unoriented or orientedfilms, filaments, and others with various shapes. The molded articlemade of thermoplastic resin composition (X2) or crosslinked productthereof may be an article in which whole body is made of thermoplasticresin composition (X2) or crosslinked product thereof, or in which atleast one portion is composed of thermoplastic resin composition (X2) ora crosslinked product thereof. For example, the molded article may be,like a laminated film, a composite with another thermoplastic resincomposition having different resin components or a composite withanother material, in which the composite has a portion made ofthermoplastic resin composition (X2) or crosslinked product thereof.

The above molded articles specifically include molded articles obtainedwith a known method as used in the first aspect of the invention.Hereinafter, the molded articles are described with reference to severalexamples.

For example, for extrusion-molded articles, there is no particularlimitation on the shapes and application products of the molded article.They include, for example, those as described in the first aspect of theinvention. Preferred examples are also the same. For example, there maybe mentioned, sheets, (unoriented) films, pipes, hoses, electrical wirecovers, tubes, and others. Especially, sheets (for example, skinmaterial, etc.), films, tubes, catheters, monofilaments, and nonwovenfabrics are preferable.

The method for molding thermoplastic resin compositions (X2) orcrosslinked products thereof by extrusion is the same as the firstaspect of the invention.

Oriented films can be obtained similarly to the case of in the firstaspect of the invention.

The draw ratio in drawing sheets or unoriented films and the thicknessof resulting oriented films are the same as those in the first aspect ofthe invention.

As the film-shaped molded article, an inflation film can be produced. Oninflation molding, drawdown is not likely to develop.

The film or film-shaped molded articles made of thermoplastic resincomposition (X2) or the crosslinked material thereof are excellent inflexibility, strength, heat resistance, stretching property, impactresistance, aging resistance, transparency, see-through property, gloss,rigidity, moisture resistance, and gas barrier property, and can bewidely used as packaging films and others.

The filament-shaped molded article is obtained in a way similar to thatin the first aspect of the invention, and may be oriented in a waysimilar to that in the first aspect of the invention. The filament madeof thermoplastic resin composition (X2) or crosslinked product thereofis excellent in transparency, flexibility, strength, heat resistance,impact resistance, and stretching property.

The nonwoven fabric is produced, specifically, by the spunbond method orthe melt-blown method. The resulting nonwoven fabric is excellent inflexibility, mechanical strength, heat resistance, impact resistance,and stretching property.

The injection-molded article can be produced in a similar way to that inthe first aspect of the invention. The injection-molded article made ofthermoplastic resin composition (X2) or crosslinked product thereof isexcellent in flexibility, transparency, strength, heat resistance,impact resistance, surface gloss, chemical resistance, abrasionresistance, and the like. It can be widely used for automobile interiortrims, automobile exterior materials, housings for home electricappliances, containers, and others.

The blow-molded article can be produced in a similar way to that in thefirst aspect of the invention. The blow-molded article made ofthermoplastic resin composition (X2) or crosslinked product thereof maybe a multilayer molded article containing at least one layer made ofthermoplastic resin composition (X2).

Extrusion blow molding and injection blow molding are conductedsimilarly to those in the first aspect of the invention. The blow-moldedarticle made of thermoplastic resin composition (X2) or crosslinkedproduct thereof is excellent in transparency, flexibility, heatresistance, impact resistance, and moisture resistance as well.

The press-molded articles include articles similar to the first aspectof the invention. Specific examples of stamping-molded articles alsoinclude articles similar to the first aspect of the invention.

The press-molded article made of thermoplastic resin composition (X2) orcrosslinked product thereof is excellent in flexibility, heatresistance, transparency, impact resistance, aging resistance, surfacegloss, chemical resistance, abrasion resistance, and others.

The molded article made of thermoplastic resin composition (X2) orcrosslinked product thereof is excellent in mechanical strength such ashardness, excellent in rubber elasticity and permanent compression setat high temperatures as well as normal temperature, and also excellentin transparency and scratch resistance. In addition, when softener (E2)is contained, the article is excellent in balance of the shape retentionand the rubber elasticity and permanent compression set, especially athigh temperatures. Furthermore, the article is easily recycled andobtained in a cost-effective manner. Therefore, thermoplastic resincomposition (X2) or crosslinked product thereof is suitable for use inautomobile interior components, automobile exterior components, homeelectric appliance components, construction or building components,wrapping sheets, cap liners, gaskets, and convenience goods;particularly, it is suitable for use in automobile interior and exteriorcomponents, for which rubber elasticity is required even at hightemperatures.

Specific examples of automobile interior components automobile exteriorcomponents, home electric appliance components, construction andbuilding components, wrapping sheets, cap liners, and convenience goodsmade of thermoplastic resin composition (X2) or crosslinked materialthereof include the same examples as described in the first aspect ofthe invention. As the method for producing the cap liners, there may bementioned a method of punching out a sheet prepared from thermoplasticresin composition of the second aspect of the invention.

The method for producing caps with the cap liners and applications ofthe cap liners and the caps with the cap liners are the same as thefirst aspect of the invention.

The molded article made of crosslinked material of thermoplastic resincomposition (X2) may be produced by molding crosslinked material ofthermoplastic resin composition (X2). Alternatively the article can alsobe produced by applying post-crosslinking with heating or irradiatingelectron beam or others to a molded article formed from thermoplasticresin composition (X2) alone or a mixture prepared by kneadingthermoplastic resin composition (X2), a crosslinker or crosslinkingauxiliary, and others.

3. Third Aspect

Hereinafter, the third aspect of the present invention is explained indetail.

<Propylene-Based Polymer (A3)>

Propylene-based polymer (A3) used in the third aspect of the inventioncontains 90 mol % or more of propylene units, is insoluble in n-decaneat 23° C., and has an intrinsic viscosity [η] of 0.01 to 10 dl/g asmeasured in decalin at 135° C. or a melt flow rate (MFR) of 0.01 to 50g/10 min as measured at 230° C. under a load of 2.16 kg in accordancewith ASTM D1238.

Propylene-based polymers (A3) include homopolypropylene and copolymersof propylene and at least one C₂-C₂₀ α-olefin except propylene. Specificexamples of the C₂-C₂₀ α-olefins except propylene include the C₂-C₂₀α-olefins used for isotactic polypropylene (A1) of the first aspect ofthe invention. Also, the preferable range is the same.

These α-olefins may form a random copolymer with propylene.

Propylene-based polymer (A3) may contain structural units derived fromsuch α-olefin in an amount of 10 mol % or less, preferably 7 mol % orless.

If necessary, a plurality of propylene-based polymers (A3) may be usedtogether. For example, two or more polymers different in melting pointor rigidity may be used.

Propylene-based polymer (A3) is insoluble in n-decane at 23° C. Suchproperty can be examined as follows.

Five grams of a sample are completely dissolved in 300 mL of n-decane at145° C. and kept for 1 hr; the resultant solution is left at roomtemperature (23° C.) for 1 hr and stirred with a rotator for additional1 hr; the solution is filtered through a 325-mesh screen; to thefiltrate is added acetone about three times by volume of the filtrate toprecipitate a polymer component dissolved in the solution; the mixtureis through a 325-mesh screen to collect the polymer component, which isregarded as then-decane-soluble component.

In the third aspect of the invention, the component that is not solublein n-decane is regarded as the n-decane-insoluble component. Thisn-decane-insoluble component corresponds to polypropylene-based polymer(A3). The n-decane-soluble component corresponds to, for example, partor all of other components or soft component (C3) described below, whichmay be optionally added.

For preparing composition (X3) of the third aspect of the invention,there may be used a polypropylene such as random PP and block PP, whichcontains both n-decane-insoluble propylene-based polymer (A3) and then-decane-soluble component. The above random PP and block PP may containthe n-decane-soluble component in an amount of generally 30 wt % orless. In this case, in analyzing decay of magnetization, the intensityof magnetization for PP multiplied by the content of then-decane-insoluble component in PP is regarded as the intensity ofmagnetization for component (A3). Note that, f_(B) is calculated basedon the content of component (B3) and the content of component (A3) inPP, that is, the content of the n-decane-insoluble component containedin PP.

It is desirable that propylene-based polymer (A3) has an intrinsicviscosity [η] of 0.01 to 10 dl/g, and preferably 1.2 to 5.0 dl/g asmeasured in decalin at 135° C., or a melt flow rate (MFR) of 0.01 to 50g/10 min, and preferably 0.3 to 30 g/10 min as measured at 230° C. undera load of 2.16 kg in accordance with ASTM D1238.

The melting point of propylene-based polymer (A3) measured with adifferential scanning calorimeter is generally 100° C. or higher,preferably 110 to 170° C., and more preferably 110 to 150° C.

Propylene-based polymer (A3) may be isotactic or syndiotactic, but theisotactic structure is preferred considering heat resistance and others.

To obtain polypropylene-based polymer composition (X3) containingpropylene-based polymer (A3) insoluble in decane at 23° C.,homopolypropylene excellent in heat resistance or homopolypropylenecontaining the propylene-based polymer (A3) insoluble in decane at 23°C. may be also used. A block polypropylene (known block polypropylene,having generally 3 to 30 wt % of n-decane-soluble rubber components)with well-balanced heat resistance and flexibility as long as itcontains propylene-based polymer (A3) insoluble in decane at 23° C. maybe also used. Propylene/α-olefin random copolymer (except softpropylene/α-olefin random copolymer (B3)) with well-balanced flexibilityand transparency as long as it contains propylene-based polymer (A3)insoluble in decane at 23° C. may be used.

There is no particular limitation on the polypropylene containingpropylene-based polymer (A3), but it is desirable that the content ofthe components insoluble in decane at 23° C. is generally 70 wt % ormore, preferably 80 wt % or more, and more preferably 87 wt % or more.

There is no particular limitation on the polypropylene containingpropylene-based polymer (A3), but it is desirable and the melting peakobserved with a differential scanning calorimeter (DSC) is generally100° C. or higher, and preferably 110 to 150° C.

The polypropylene containing propylene-based polymer (A3) can beproduced in a similar way to that in producing isotactic polypropylene(A1) used in the first aspect of the invention.

<Soft Propylene/α-Olefin Random Copolymer (B3)>

Soft propylene/α-olefin random copolymer (B3) used in the third aspectof the invention satisfies all of requirements (b3-1) to (b3-5) below.

(b3-1) The intrinsic viscosity [η] measured in decalin at 135° C. is0.01 to 10 dl/g, and preferably 0.05 to 10 dl/g.

(b3-2) The melting point is lower than 100° C., and preferably nothigher than 60° C. or not observed when measured with a differentialscanning calorimeter (DSC), wherein “melting point is not observed”means that any melting endothermic peak of crystal with a meltingendothermic entalpy of crystal of 1 J/g or more is not observed in thetemperature range of −150 to 200° C. The measurement conditions are asdescribed in Examples of the third aspect of the invention.

(b3-3) The content of propylene-derived structural units is 60 to 75 mol%, and preferably 56 to 73 mol %; the content of ethylene-derivedstructural units is 10 to 14.5 mol %, and preferably 12 to 14 mol %; andthe content of C₄-C₂₀ α-olefin-derived structural units is 10.5 to 30mol %, and preferably 15 to 25 mol %. As the α-olefin, 1-butene isparticularly preferable.

(b3-4) Triad tacticity (mm-fraction) determined by ¹³C-NMR is 85% to97.5%, preferably 87% to 97%, and more preferably 90% to 97%. With theabove range of mm-fraction, the flexibility and mechanical strength areparticularly well-balanced, which is desirable for the third aspect ofthe invention. The mm-fraction can be determined in accordance with themethod as described in WO 04/087775 from Page 21 line 7 to Page 26 line6.

(b3-5) Molecular weight distribution (Mw/Mn, relative to polystyrenestandards, Mw: weight-average molecular weight, Mn: number-averagemolecular weight) measured by gel permeation chromatography (GPC) is 1.0to 3.0, and preferably 2.5 or less. The molecular weight distributionwithin the above range indicates that soft propylene/α-olefin randomcopolymer (B3) is composed of polymer chains with a uniform structure.With soft propylene/α-olefin random copolymer (B3) composed of polymerchains with a uniform structure, on heat treatment of molded articles athigh temperatures (100° C. or higher), whitening can be suppressed moreeffectively than the case using a soft propylene/α-olefin randomcopolymer with a wider molecular weight distribution.

Desirable embodiments of soft propylene/α-olefin random copolymer (B3)have independently the following additional properties.

Soft propylene/α-olefin random copolymer (B3) is preferably the same aspropylene/ethylene/α-olefin copolymer (B1) of the first aspect of theinvention in the stress at 100% elongation (M100), crystallinity, andglass transition temperature Tg. These properties exhibit the sameeffects.

When soft propylene/α-olefin random copolymer (B3) shows a melting point(Tm in ° C.) in the endothermic curve obtained with a differentialscanning calorimeter (DSC), the melting endothermic entalpy ΔH isgenerally 30 J/g or less and also satisfies the same relation between C₃(propylene) content (mol %) and ΔH (J/g) as that ofpropylene/ethylene/α-olefin copolymer (B1) used in the first aspect ofthe invention.

The Shore A hardness of soft propylene/α-olefin random copolymer (B3) isgenerally 30 to 80, and preferably 35 to 70.

Soft propylene/α-olefin random copolymer (B3) desirably has a melt flowrate (MFR) in the range of 0.01 to 50 g/10 min, and preferably 0.05 to40 g/10 min, as measured at 230° C. under a load of 2.16 kg inaccordance with ASTM D1238.

When soft propylene/α-olefin random copolymer (B3) is used, regardlessof the type of propylene-based polymer (A3), resultant propylene-basedpolymer composition (X3) exhibits excellent whitening resistance,transparency, flexibility, heat resistance, and stretching property,which is suitable for the third aspect of the invention.

Soft propylene/α-olefin random copolymer (B3) can be produced, forexample, by the method described in WO 04/87775.

<Propylene-Based Polymer Composition (X3)>

Propylene-based polymer composition (X3) of the third aspect comprisespropylene-based polymer (A3) in an amount of 10 to 98 wt %, preferably20 to 95 wt %, and more preferably 50 to 93 wt %; and softpropylene/α-olefin random copolymer (B3) in an amount of 2 to 90 wt %,preferably 5 to 80 wt %, and more preferably 7 to 50 wt % wherein thetotal of (A3) and (B3) is 100 wt %.

In a preferred embodiment of propylene-based polymer composition (X3),intensites of magnetization decaying due to transverse relaxation ofpropylene-based polymer (A3), soft propylene/α-olefin random copolymer(B3), and propylene-based polymer composition (X3-1) described beloweach measured to 1000 μs in pulse NMR measurements (Solid-echoexperiment, observed for ¹H) satisfy relation (3-1) below in the entirerange of t (observing time) from 500 to 1000 μs:

M(t)_(A)×(1−f _(B))+M(t)_(B) X× _(B) −M(t)_(X-1)≧0.02  3-1

M(t)_(A): the intensity of magnetization in decay process at time tmeasured for propylene-based polymer (A3) used in propylene-basedpolymer composition (X3),

M(t)_(B): the intensity of magnetization in decay process at time tmeasured for soft propylene/α-olefin random copolymer (B3) used inpropylene-based polymer composition (X3),

M(t)_(X-1): the intensity of magnetization in decay process at time tmeasured for propylene-based polymer composition (X3-1), which isprepared by melt-kneading soft propylene/α-olefin random copolymer (B3)used in propylene-based polymer composition (X3) and polypropylenecontaining propylene-based polymer (A3) used in propylene-based polymercomposition (X3) in the same ratio at that in propylene-based polymercomposition (X3), and

f_(B): the weight ratio of soft propylene/α-olefin random copolymer (B3)to the total of propylene-based polymer (A3) and soft propylene/α-olefinrandom copolymer (B3) in propylene-based polymer composition (X3);0.02≦f_(B)≦0.90,

wherein t (observation time) is 500 to 1000 μs; each of M(t)_(A),M(t)_(B), and M(t)_(X-1) is normalized into 0 to 1 (the maximummagnitude is set to be 1).

Composition (X3-1) is prepared as follows: polypropylene containingpropylene-based polymer composition (X3) used in propylene-based polymer(X3) and soft propylene/α-olefin random copolymer (B3) used inpropylene-based polymer composition (X3) are melt-kneaded so that theratio of polymer (A3) and copolymer (B3) is the same as that inpropylene-based polymer composition (X3). The polypropylene containingpropylene-based polymer (A3) may be composed only of propylene-basedpolymer (A3) or may contain, as described above, components other thanpropylene-based polymer (A3), for example, the component soluble indecane at 23° C., in an amount of 30 wt % or more of the polypropylene.

The above composition is obtained by using a known melt-kneader at 160to 300° C. Specifically, there may be mentioned a method in which sourcematerials are loaded in an amount of 70 vol % or more in a Laboplast-mill (for example, manufactured by Toyo Seiki Seisaku-Sho, Ltd.)and kneaded at 160 to 250° C. with 30 rpm to 100 rpm for 3 min or more;and the kneaded material is air-cooled to obtain the desiredcomposition.

Hereinafter, the conditions for the pulse NMR measurement and thedefinition of decay curves are explained.

In the third aspect of the invention, the decay curve M(t) representsthe behavior of magnetization generally called spin-spin relaxation. Thedecay curve, which represents the relation of the intensity ofmagnetization “M” versus the observation time “t” (0 to 1000 μs), can beobtained under the following conditions in the pulse NMR measurement.

Sample preparation: about 0.5 g of a sample is loaded in a 10-mmΦ glasstube

Frequency: proton resonance frequency at 25 MHz

Method: Solid-echo sequence

-   -   90°-pulse: 2.0 μs, pulse delay: 4 s, and number of scans: 8

Measuring temperature: 100° C.

Details for decay curve M(t) are described in “Kakujiki Kyomei No KisoTo Genri” (1987) p. 258 by Ryuzo Kitamaru, Kyoritsu Shuppan; andKubo, R.and Tomita, K., J. Phys. Soc. Jpn., 9(1954), 888.

The decay curve M(t) ranges from 0 to 1, because it is normalized on thebasis of its maximum value.

Although the reason is unclear why preferred composition (X3) can beobtained when the above relation is satisfied, the present inventorsconsider as follows. M(t) is an index representing the motion of thepolymer molecular chains, and if there were no molecular levelinteraction between propylene-based polymer (A3) and softpropylene/α-olefin random copolymer (B3) in a propylene-based polymercomposition, inequality (3-1) would be approximately reduced to thefollowing equation:

M(t)_(A)×(1−f _(B))+M(t)_(B) ×f _(B) =M(t)_(X-1)  3-1-2

If there are molecular level interactions between propylene-basedpolymer (A3) and soft propylene/α-olefin random copolymer (B3) in thepropylene-based polymer composition, the molecular motion of components(A3) and (B3) will change. In particular, when the molecular motion ofsoft propylene/α-olefin random copolymer (B3) with a quite lowcrystallinity is constrained by the interaction, the decay of themagnetization for the propylene-based polymer composition becomes fast,and hence, formula (3-1) is satisfied.

With the propylene polymer composition satisfying the above relation,molded articles thereof not suffer from separation or break betweenpropylene-based polymer (A3) and soft propylene/α-olefin randomcopolymer (B3) even when deformation or impact is applied to thearticle, and therefore it is likely to exhibit excellent whiteningresistance, scratch resistance, heat resistance, and stretching propertywhile retaining flexibility. In addition, because crystallinepropylene-based polymer (A3) and non-crystalline soft propylene/α-olefinrandom copolymer (B3) are mixed well in the composition, when the moldedarticle of the composition is kept at high temperatures (annealed),whitening of the molded article caused by the growth of crystallinecomponent during annealing is likely to be suppressed.

In the third aspect of the invention, composition (X3-1) satisfiespreferably formula (3-1-3), and more preferably formula (3-1-4) below:

{M(t)_(A)×(1−f _(B))+M(t)_(B) ×f _(B) }−M(t)_(X-1)>0.04  3-1-3,

{M(t)_(A)×(1−f _(B))+M(t)_(B) ×f _(B) }−M(t)_(X-1)>0.05  3-1-4,

wherein, t is 500 to 1000 μs.

When propylene-based polymer composition (X3) further has the propertyspecified by formula (3-2) below besides the above properties, themolded article thereof is well-balanced flexibility and mechanicalstrength, and suitable for use in the third aspect of the invention.Furthermore, composition (X3) satisfies preferably formula (3-2-2), andmore preferably formula (3-2-3) below.

TS _(X-1)≧35f _(B) +TS ₀  (3-2),

TS _(X-1)≧−30f _(B) +TS ₀  (3-2-2),

TS _(X-1)≧−25f _(B) +TS ₀  (3-2-3),

TS_(X-1): strength at break of propylene-based polymer composition(X3-1) obtained by melt-kneading propylene-based polymer (A3) andpropylene/α-olefin random copolymer (B3) at the same weight ratio asthat in propylene-based polymer composition (X3),

TS₀: strength at break of propylene-based polymer (A3) used inpropylene-based polymer composition (X3), and

f_(B): composition ratio of soft propylene/α-olefin random copolymer(B3) (0.02≦f_(B)≦0.90).

Whether these relations are satisfied or not is examined, for example,by using a 2-mm thick pressed sheet obtained under the followingpress-molding conditions at a tensile speed of 200 mm/min in accordancewith JIS K7113-2.

Press-molding conditions:

heating time: 5 to 7 min,

heating temperature: 190 to 250° C.,

pressure on heating: 0.1 MPa or higher, and

cooling speed: 200° C./5 min or higher (cooling down to room temperaturein 5 min).

When propylene-based polymer composition (X3) of the third aspect of theinvention further has a property represented by formula (3-3) belowbesides the above properties, the molded article thereof has excellentwhitening resistance and recovery property; thus such composition ispreferred. The composition satisfies preferably formula (3-3-2), andmore preferably formula (3-3-3).

EL(YS)≧EL(YS)₀ +f _(B)×15  (3-2)

EL(YS)≧EL(YS)₀ +f _(B)×17  (3-2-2)

EL(YS)≧EL(YS)₀ +f _(B)×20  (3-2-3)

EL(YS): elongation where yield stress is attained in the tensile test(elongation at yield) of propylene-based polymer composition (X3-1)obtained by melt-kneading propylene-based polymer (A3) and softpropylene/α-olefin random copolymer (B3) at the same ratio as that inpropylene-based polymer composition (X3)

EL(YS)₀: elongation where yield stress is attained in the tensile test(elongation at yield) of propylene-based polymer (A3) used inpropylene-based polymer composition (X3).

f_(B): composition ratio of soft propylene/α-olefin random copolymer(B3) (0.02≦f_(B)≦0.90)

Whether these relations are satisfied or not is examined, for example,by testing a 2-mm thick press-molded sheet obtained under the followingpress-mold conditions at a tensile speed of 200 mm/min in accordancewith JIS K7113-2.

Press-mold conditions:

heating time: 5 to 7 min,

heating temperature: 190° C. to 250° C.,

heating pressure: 0.1 MPa or higher, and

cooling speed: 200° C./5 min or higher (cooling to room temperature in 5min)

Note that when the propylene-based polymer composition has no yieldpoint, the composition is regarded as satisfying the propertyrepresented by formula 3-3.

Propylene-based polymer composition (X3) is produced with a knownkneader as in the first aspect of the invention. Preferable methods arealso the same.

<Ethylene-Based Polymer and Styrene-Based Polymer (C3)>

Propylene-based polymer composition (X3) of the third aspect of theinvention may further contain at least one polymer (soft component) thatis selected from ethylene-based polymer and styrene-based polymer andhas a Shore A hardness of 95 or less and/or a Shore D hardness of 60 orless. Shore A hardness and Shore D hardness are measured with a 2-mmthick press-molded sheet that is prepared at a press temperature of 190°C., cooled to room temperature, and left at 23° C. for 3 days beforemeasurement.

A polymer having a Shore A hardness of 20 or more is more preferable.

Specific examples of the ethylene-based polymer or styrene-basedpolymers include styrene-based elastomers, ethylene/α-olefin randomcopolymers, ethylene/vinyl acetate copolymers, ethylene/acrylic acidcopolymers, ethylene/methyl methacrylate copolymers, and others. Astyrene-based elastomer (C3-1) and ethylene/α-olefin random copolymer(C3-2) below are preferably used.

Specific examples of styrene-based elastomer (C3-1) include hydrogenateddiene polymers comprising polybutadiene block segments and styrene typecompound (including styrene itself, the same applieshereinafter)/butadiene copolymer block segments, hydrogenated dienepolymers comprising polyisoprene block segments and styrene typecompound/isoprene copolymer block segments, block copolymers comprisingpolymer blocks mainly derived from a styrene type compound and polymerblocks mainly derived from a conjugated diene; hydrogenated products ofrandom copolymers of styrene type compound and conjugated diene,hydrogenated derivatives of block copolymers comprising polymer blocksmainly derived from a styrene type compound and polymer blocks mainlyderived from a conjugated diene; and others. Known elastomers may beused without limitation. Styrene-based elastomer (C3-1) may be usedalone or in combination.

Styrene-based elastomer (C3-1) may be oil-extended. For example,styrene-based elastomer (C3-1) can incorporate a publicly known paraffinoil having a kinematic viscosity at 40° C. of 20 to 800 cSt andpreferably 40 to 600 cSt, a pour point of 0 to −40° C. and preferably 0to −30° C., and a flash temperature (COC test) of 200 to 400° C. andpreferably 250 to 350° C. Thus, incorporating the paraffin oilsignificantly improves flexibility of molded articles. The amount of theparaffin oil to be added is preferably 10 to 150 parts by weightrelative to 100 parts by weight of styrene-based elastomer (C3-1) beforeoil-extended. In this case, combination of styrene-based elastomer(C3-1) before oil-extended and the oil is regarded as one styrene-basedelastomer. The oil may be separately added to propylene-based polymercomposition (X3). In this case, the oil is also regarded as one of thecomponents of polymer (C3).

Ethylene/α-olefin random copolymer (C3-2) refers to a copolymer obtainedby copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms,preferably 3 to 10 carbon atoms, and the copolymer with the followingproperties is preferably used:

(a) the density at 23° C. in accordance with ASTM 1505 is in the rangeof 0.850 to 0.910 g/cm³, preferably 0.860 to 0.905 g/cm³, and morepreferably 0.865 to 0.895 g/cm³; and

(b) the MFR at 190° C. under a load of 2.16 kg is in the range of 0.1 to150 g/10 min and preferably 0.3 to 100 g/10 min.

The crystallinity of ethylene/α-olefin random copolymer determined byX-ray diffractometry is 40% or less, preferably 0 to 39%, and morepreferably 0 to 35%.

Specific examples of the C₃-C₂₀ α-olefin used as the co-monomer includepropylene, 1-butene, 1-pentene, 1-hexene, 4-methylpent-1-ene, 1-octene,1-decene, and 1-dodecene. These co-monomers may be used alone or incombination. Among them, propylene, 1-butene, 1-hexene, and 1-octene arepreferable. If necessary, a small amount of another co-monomer, forexample, a diene such as 1,6-hexadiene and 1,8-octadiene, a cycloolefinsuch as cyclopentene, or others may be used. The α-olefin content in thecopolymer is generally 3 to 50 mol %, preferably 5 to 30 mol %, and morepreferably 5 to 25 mol %.

The molecular structure of the copolymer may be linear or branched withlong or short side-chains. Further, a plurality of differentethylene/α-olefin random copolymers may be used as a mixture.

The methods for producing ethylene/α-olefin random copolymer (C3-2) arenot particularly limited, but include a known method using a vanadiumcatalyst, a titanium catalyst, a metallocene catalyst, or the like. Inparticular, the copolymer produced using a metallocene catalyst has amolecular weight distribution (Mw/Mn) of generally 3 or lower, and issuitable for use in the third aspect of the invention.

Ethylene/α-olefin random copolymer (C3-2) may be oil-extended. Forexample, known paraffin oil as described above can be incorporated intoethylene/α-olefin random copolymer (C3-2), and addition of paraffin oilsignificantly improves the flexibility of molded articles. The amount ofparaffin oil to be added is preferably 10 to 150 parts by weightrelative to 100 parts by weight of ethylene/α-olefin random copolymer(C3-2) before oil-extended. In this case, the combination ofethylene/α-olefin random copolymer (C3-2) before oil-extended and theoil is regarded as one ethylene/α-olefin random copolymer (C3-2). Oilmay be separately added to propylene-based polymer composition (X3). Inthis case, the oil is also regarded as one of the components of polymer(C3).

When one or more polymers (C3) selected from ethylene-based polymers andstyrene-based polymers are used, the amount thereof is not particularlylimited; the total of one or more polymers (C3) selected fromethylene-based polymers and styrene-based polymers is generally 1 to 40parts by weight, preferably 5 to 30 parts by weight, and more preferably5 to 20 parts by weight, relative to 100 parts by weight of the total ofpropylene-based polymer (A3) and propylene/α-olefin copolymer (B3).Addition of such polymer (C3) is preferred, because the compositionprovides molded articles with improved impact resistance.

Propylene-based polymer composition (X3) may contain other resinsbesides (A3), (B3), and (C3), other rubbers besides (A3), (B3), and(C3), known adhesion improvers, or the additives as described in thefirst aspect of the invention, unless the objects of the third aspect ofthe invention are impaired. The amount of these components is notlimited within such range that the objects of the third aspect of theinvention are not impaired. In one embodiment, the amount is 40 parts byweight or less and preferably 20 parts by weight or less, relative to100 parts by weight of the total of propylene-based polymer (A3), softpropylene/α-olefin random copolymer (B3), and, if any, one or morepolymer (C3) selected from ethylene-based polymers and styrene-basedpolymers.

Particularly, in applications where a known pigment is added forcoloring, propylene-based polymer composition (X3) of the third aspectof the invention is suitable, because it provides molded articles withexcellent whitening resistance.

The molded article of the third aspect of the invention is produced frompropylene-based polymer composition (X3) using a known molding methodsuch as blow molding, injection molding, extrusion molding, andinflation molding. Specific examples of the molded articles related tothe third aspect include blow-molded articles, injection-moldedarticles, extrusion-molded articles including films and sheets,inflation-molded articles, tubes, and others. More particularly, theyinclude containers such as infusion solution bottles, food cups, foodbottles, sanitary bottles such as shampoo bottles, cosmetics bottles,and tubes; sheets or films such as food packaging films, electroniccomponent-packaging films, and other packaging sheet or films; caps,home electric appliance housings, automobile components, conveniencegoods, stationery, and others.

Among them preferred are blow-molded or injection-molded containers,injection-molded articles, extrusion-molded sheets, films or tubes, andinflation-molded sheets or films.

Another preferred example of the molded article related to the thirdaspect is a wrap film for foods (food packaging material in a form ofwrap film).

The wrap film for foods is a single-layer or multilayer film having atleast one layer of the molded article of the third aspect of theinvention.

Multilayer configuration may be adopted to attain properties other thanthe effects of the third aspect of the invention, such as cuttingproperty and stickiness. The resin components to form a layer other thanthe layer formed from propylene-based polymer composition (X3) includepolypropylene, high-density polyethylene, low-density polyethylene,linear low-density polyethylene, ultra-low-density polyethylene, nylon,poly(4-methyl-1-pentene), ethylene/vinyl acetate copolymer, and others.Preferred are ethylene-based copolymers containing 70 mol % or more ofethylene units.

The thickness of the wrap film for foods related to the third aspect isnot particularly limited to, but generally 5 to 50 μm and preferably 8to 30 μm in view of film strength, flexibility, and transparency.

The film related to the third aspect is produced using a single-layer ormultilayer T-die molding machine or an inflation molding machineconventionally used for molding polyolefin films.

In order to adjust stickiness and anti-clouding property, the food wrapfilm of the third aspect may contain a known tackifier or surfactant.The tackifiers include liquid hydrocarbons such as polybutene and anolefin oligomer, liquid paraffin, aliphatic petroleum resins, alicyclicpetroleum resins, and the like. The surfactants include glycerin fattyacid monoesters, glycerin fatty acid esters, sorbitan fatty acid esters,and the like. These may be used alone or as a mixture of two or more.

In the food wrap film of the third aspect, when at least the layer madeof propylene-based polymer composition (X3) is uniaxially or biaxiallyoriented, the film has excellent nerve and has no yield point whileretaining the above properties. The lack of yield point indicates thatthe film retains sufficient stress and tension, for example, when it isstretched to cover a container or the like, and hence the film issuitable for wrapping. The draw ratio is not particularly limited; forexample, in uniaxial orientation, the desired draw ratio is 1.2 to 5.0and preferably 1.5 to 3.5. In biaxial orientation, it is desired thatthe longitudinal draw ratio is 1.2 to 5.0 and preferably 1.5 to 3.5 andthe transverse one is 1.2 to 5.0 and preferably 1.5 to 3.5.

The food wrap film using propylene-based polymer composition (X3) hasexcellent heat resistance, transparency, and whitening resistance.

Another preferred example of the molded article related to the thirdaspect is a cap liner, which has at least one layer made ofpropylene-based polymer composition (X3).

4. Fourth Aspect

Hereinafter, the fourth aspect of the present invention is explained indetail.

<Isotactic Polypropylene (A4)>

Isotactic polypropylenes (A4) used in the fourth aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. Specific examples of the C₂-C₂₀ α-olefinsexcept propylene include the same as those for isotactic polypropylene(A1) used in the first aspect. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

Structural units derived from such α-olefin may be contained in a ratioof 10 mol % or less, preferably 7 mol % or less, in all monomersincluding propylene.

Isotactic polypropylene (A4) preferably has the same properties as thoseof isotactic polypropylene (A1) used in the first aspect concerningisotactic pentad fraction (mmmm) and melt flow rate (MFR).

There may be used, if necessary, a plurality of isotactic polypropylenes(A4) together, for example, two or more components different in meltingpoint or rigidity.

To attain desired properties, there may be used, as isotacticpolypropylene (A4), one or more polypropylenes selected fromhomopolypropylene with excellent heat resistance (publicly known,generally containing 3 mol % or less of comonomer except propylene),block polypropylene with excellent balance of heat resistance andflexibility (publicly known, generally containing 3 to 30 wt % ofn-decane-soluble rubber components), and random polypropylene withexcellent balance of flexibility and transparency (publicly known,generally having a melting peak of 100° C. or higher and preferably inthe range of 115° C. to 160° C. as measured with a differential scanningcalorimeter (DSC)).

Such isotactic polypropylene (A4) can be produced similarly to isotacticpolypropylene (A1) used in the first aspect.

<Propylene/Ethylene/α-Olefin Copolymer (B4)>

Propylene/ethylene/α-olefin copolymer (B4) used in the fourth aspect ofthe invention is a copolymer with at least one C₂-C₂₀ α-olefin exceptpropylene and its melting point is lower than 100° C. and preferably notobserved when measured with a differential scanning calorimeter DSC.Here, the expression “melting point is not observed” means that anymelting endothermic peak of crystal having a melting endothermic entalpyof crystal of 1 J/g or more is not observed in the temperature range of−150 to 200° C. The measurement conditions are as described in Examplesof the fourth aspect of the invention.

In propylene/ethylene/α-olefin copolymer (B4), the content ofpropylene-derived structural units is 40 to 85 mol %, preferably 58 to80 mol %, and more preferably 58 to 74 mol %; the content ofethylene-derived structural units is 5 to 30 mol %, preferably 10 to14.5 mol %, and more preferably 11 to 14.5 mol %; and the content ofC₄-C₂₀ α-olefin-derived structural units is 5 to 30 mol %, preferably 10to 27.5 mol %, and more preferably 15 to 27.5 mol %.

Propylene/ethylene/α-olefin copolymer (B4) containing thepropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀ α-olefin-derived structural units at the above ratio hasexcellent compatibility with isotactic polypropylene (A4), andtherefore, the resulting propylene-based polymer composition is likelyto exhibit excellent transparency, flexibility, heat resistance, andscratch resistance.

When the contents of structural units derived from propylene, ethylene,and a C₄-C₂₀ α-olefin are in the preferable ranges,propylene/ethylene/α-olefin copolymer (B4) attains more excellentbalance of heat resistance and scratch resistance. More specifically,the copolymer with a more satisfactory ethylene content providesoriented films with excellent transparency and impact resistance; andthe copolymer with a more satisfactory α-olefin content providesoriented films with excellent flexibility as well as transparency andimpact resistance. Therefore, such copolymer can be suitably used in thefourth aspect.

Among the C₄-C₂₀ α-olefins, 1-butene is especially preferable in thefourth aspect of the invention.

Propylene/ethylene/α-olefin copolymer (B4) preferably has the sameproperties as propylene/ethylene/α-olefin copolymer (B1) used in thefirst aspect of the invention concerning intrinsic viscosity [n],crystallinity, glass transition temperature Tg, molecular weightdistribution (Mw/Mn), and triad tacticity (mm-fraction). Effects ofthese properties are also similar.

For instance, propylene/ethylene/α-olefin copolymer (B4) has themolecular weight distribution (Mw/Mn, relative to polystyrene standards,Mw: weight-average molecular weight, Mn: number-average molecularweight) of 4.0 or less, preferably 3.0 or less, and more preferably 2.5or less as measured with GPC.

The triad tacticity (mm-fraction) of the propylene/ethylene/α-olefincopolymer (B4) measured by ¹³C-NMR is preferably 85% or more, morepreferably 85% to 97.5%, still more preferably 87% to 97%, andparticularly preferably 90% to 97%. With the above range of triadtacticity, the balance of flexibility and mechanical strength isparticularly excellent, which is suitable for the fourth aspect of theinvention. The mm-fraction can be determined by the method described inWO 04/087775 from Page 21 line 7 to Page 26 line 6.

When propylene/ethylene/α-olefin copolymer (B4) has a melting point (Tmin ° C.) in the endothermic curve measured with a differential scanningcalorimeter (DSC), the melting endothermic entalpy ΔH is generally 30J/g or less, and the same relation between the C3 content (mol %) andmelting endothermic entalpy ΔH (J/g) is satisfied as withpropylene/ethylene/α-olefin copolymer (B1) used in the first aspect ofthe invention.

In the fourth aspect of the invention, the propylene/ethylene/α-olefincopolymer (B4) exhibiting no melting point is more preferred.

Propylene/ethylene/α-olefin copolymer (B4) may be partly graft-modifiedwith a polar monomer. The polar monomers include hydroxylgroup-containing ethylenically unsaturated compounds, aminogroup-containing ethylenically unsaturated compounds, epoxygroup-containing ethylenically unsaturated compounds, aromatic vinylcompounds, unsaturated carboxylic acids or derivatives thereof, vinylesters, vinyl chloride, and others.

<Resin Composition (X4)>

The film of the fourth aspect of the invention is a single-layer ormultilayer film having at least one layer made of resin composition (X4)containing (A4) and (B4), wherein the layer of the resin composition isat least uniaxially or biaxially oriented. Resin composition (X4) usedin the fourth aspect contains (A4) and (B4) below:

isotactic polypropylene (A4) in an amount of 10 to 97 wt %, preferably50 to 95 wt %, and more preferably 55 to 95 wt %; andpropylene/ethylene/α-olefin copolymer (B4) in an amount of 3 to 90 wt %,preferably 5 to 50 wt %, and more preferably 5 to 45 wt %.

If the contents of (A4) and (B4) were out of the above ranges, it wouldbe difficult to form into an oriented film, and the film would havestretching property and significantly lowered nerve.

In order to improve the heat shrink ratio of the film related to thefourth aspect, there may be added hydrocarbon resin (C4) having asoftening point of 50° C. to 160° C. as measured with the ring-and-ballmethod in accordance with ASTM-D36 and a number-average molecular weightof 300 to 1400 as measured with GPC. Specific examples of hydrocarbonresins (C4) include publicly known petroleum resin (aliphatichydrocarbon resin, aromatic hydrocarbon resin, alicyclic hydrocarbonresin, hydrogenated derivatives thereof, etc.), rosin, rosin ester,terpene resin, and hydrogenated derivatives thereof.

The amount of hydrocarbon resin (C4) added is preferably 3 to 70 partsby weight, and more preferably 5 to 50 parts by weight, relative to 100parts by weight of resin composition (X4) composed of (A4) and (B4).With the amount in this range, the impact resistance of film is rarelylowered.

In order to further improve the impact resistance of the film related tothe fourth aspect, there may be added publicly known ethylene/α-olefinrandom copolymer. This ethylene/α-olefin random copolymer preferably hasthe same properties as those of ethylene/α-olefin random copolymer (D1)used in the first aspect concerning density and MFR.

There is no particular limitation on the method for producing suchethylene/α-olefin random copolymer. The copolymer can be produced bycopolymerizing ethylene and the α-olefin with a radical polymerizationcatalyst, a Philips catalyst, a Ziegler-Natta catalyst, or a metallocenecatalyst. In particular, the copolymer produced with a metallocenecatalyst has a molecular weight distribution (Mw/Mn) of generally 3 orless and is suitably used for the fourth aspect.

The amount of ethylene/α-olefin random copolymer added is preferably 1to 30 parts by weight and more preferably 3 to 20 parts by weight,relative to 100 parts by weight of resin composition (X4) composed of(A4) and (B4). In the case of putting a high priority in filmtransparency, 20 parts by weight or less is preferable.

To resin composition (X4) there may also be added other resins, otherrubbers, inorganic filler, and the like, and also additives as with thefirst aspect, as long as the objectives of the fourth aspect are notimpaired. For resin composition (X4), the amounts of such other resins,other rubbers, inorganic filler, additives, and others are notparticularly limited as long as the objectives of the fourth aspect arenot impaired. In one embodiment, the total of isotactic polypropylene(A4), propylene/ethylene/α-olefin copolymer (B4), if any hydrocarbonresin (C4), and if any, the ethylene/α-olefin random copolymer is 60 to100 wt %, and preferably 80 to 100 wt % of the whole composition.

<Films>

The film of the fourth aspect has at least one layer made of resincomposition (X4) containing isotactic polypropylene (A4),propylene/ethylene/α-olefin copolymer (B4), and optionally hydrocarbonresin (C4), wherein the layer made of resin composition (X4) is at leastuniaxially or biaxially oriented. The above layer can be produced bycommon molding and orientation methods for polyolefin resin films. Forexample, there may be employed a method in which a film molded bypublicly known methods such as inflation molding and T-die molding isuniaxially or biaxially oriented with a heating roll/tenter at 40° C. to180° C. and preferably 60° C. to 160° C. Simultaneous biaxialorientation with tubular molding technique may also be employed.

The draw ratio is not particularly limited to, but generally 1.5 ormore, preferably 2 to 10, and more preferably 3 to 8. Exemplaryembodiments include a uniaxially oriented film in which the draw ratiois generally 1.5 or more, preferably 2 to 10, more preferably 3 to 8;and a biaxially oriented film in which the longitudinal draw ratio isgenerally 1.5 or more, preferably 2 to 10, and more preferably 3 to 8and the transverse draw ratio is generally 1.5 or more, preferably 2 to10, and more preferably 3 to 8. The thickness of the oriented film thusobtained is generally 10 to 400 μm. In the fourth aspect, this orientedfilm can be used as a layer made of resin composition (X4).

The films of the fourth aspect with the multilayer structure include anembodiment in which (an)other film(s) is/are laminated on one side orboth sides of the above film. The films to be laminated are notparticularly limited to, but include films made of polyolefin such aspolyethylene, polypropylene, polybutene, polycycloolefin resin,ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, andethylene/methyl methacrylate copolymer; styrene-based resin film; filmsmade of polyester such as polyethylene terephthalate and polybutyleneterephthalate; films made of polyamide such as nylon-6 and nylon-6,6;ethylene/vinyl alcohol copolymer film; and others. As a laminate ofadhesive polyolefin and gas-barrier resin, there may be mentioned, forexample, a laminate of maleic anhydride-modified polyethylene andethylene/vinyl alcohol copolymer. Such another film is preferably auniaxially or biaxially oriented film, but it is not limited thereto.

Said (an)other film(s) in the multilayer film may be produced, forexample, by laminating another film described above with an unorientedfilm made of resin composition (X4) and subsequently orientating thelaminate or by bonding another film to a single-layer oriented filmrelated to the fourth aspect that is formed in advance.

The film of the fourth aspect can be also prepared by producing asingle-layer or multilayer film (unoriented film) having at least onelayer made of resin composition (X4) containing (A4), (B4), andoptionally hydrocarbon resin (C4) below, followed by orientating withthe above orientation process:

10 to 97 wt % of isotactic polypropylene (A4);

3 to 90 wt % of propylene/ethylene/α-olefin copolymer (B4) that contains40 to 85 mol % of propylene-derived structural units, 5 to 30 mol % ofethylene-derived structural units, and 5 to 30 mol % of C₄-C₂₀α-olefin-derived structural units (a4), the melting point of (B4) beinglower than 100° C. or not observed when measured with a differentialscanning calorimeter, wherein the total of (A4) and (B4) is 100 wt %.

<Use>

The films of the fourth aspect are preferably used for, for example,heat-shrinkable package materials, heat-shrinkable labels, and the like.

5. Fifth Aspect

Hereinafter, the fifth aspect of the present invention is explained indetail.

<Isotactic Polypropylene (A5)>

Isotactic polypropylenes (A5) used in the fifth aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. Specific examples of the C₂-C₂₀ α-olefinsexcept propylene include the same as those for isotactic polypropylene(A1) used in the first aspect. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

The structural units derived from these α-olefins may be contained in anamount of 35 mol % or less and preferably 30 mol % or less of the wholestructural units composing isotactic polypropylene (A5).

The melting point of isotactic polypropylene (A5) measured with adifferential scanning calorimeter (DSC) is 120° C. or higher, preferably120 to 170° C., and more preferably 130 to 160° C.

There may be used, if necessary, a plurality of isotactic polypropylenes(A5) together, for example, two or more components different in meltingpoint or rigidity.

Isotactic polypropylene (A5) preferably has the same properties asisotactic polypropylene (A1) used in the first aspect concerningisotactic pentad fraction (mmmm) and melt flow rate (MFR).

Such isotactic polypropylene (A5) can be produced similarly to isotacticpolypropylene (A1) used in the first aspect.

<Propylene-Based Polymer (B5)>

Propylene-based polymers (B5) used in the fifth aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. Specific examples of the C₂-C₂₀ α-olefinsexcept propylene include the same as those for isotactic polypropylene(A5). Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

In propylene polymer (B5), the content of propylene-derived structuralunits is generally 40 to 100 mol %, preferably 40 to 99 mol %, morepreferably 40 to 92 mol %, and still more preferably 50 to 90 mol %; andthe content of structural units derived from the C₂-C₂₀α-olefin (exceptpropylene), which is used as a co-monomer, is generally 0 to 60 mol %,preferably 1 to 60 mol %, more preferably 8 to 60 mol %, and still morepreferably 10 to 50 mol %, wherein the total of propylene units andC₂-C₂₀ α-olefin units is 100 mol %.

Propylene-based polymer (B5) generally has a melt flow rate (MFR) of 0.1to 50 g/10 min as measured at 230° C. under a load of 2.16 kg inaccordance with ASTM D1238.

The melting point of propylene polymer (B5) measured with a differentialscanning calorimeter (DSC) is lower than 120° C. or not observed, andpreferably not higher than 100° C. or not observed. Here, “melting pointis not observed” means that any melting endothermic peak of crystalhaving a melting endothermic entalpy of crystal of 1 J/g or more is notobserved in the temperature range of −150 to 200° C. The measurementconditions are as described in Examples of the fifth aspect.

The intrinsic viscosity [η] of propylene-based polymer (B5) is generally0.01 to 10 dl/g, and preferably 0.05 to 10 dl/g, as measured in decalinat 135° C.

The method for producing propylene-based polymer (B5) is notparticularly limited. It can be produced by polymerizing propylene orcopolymerizing propylene and another α-olefin in the presence of apublicly known catalyst that can stereospecifically yield isotactic orsyndiotactic polyolefin, for example, a catalyst containing a solidtitanium component and an organometallic compound as major components,or a metallocene catalyst containing a metallocene compound as one ofthe catalyst components. Propylene-based polymer (B5) may be produced bypolymerizing propylene or copolymerizing propylene and another α-olefinusing a publicly known catalyst capable of providing an atacticpolyolefin. It is preferred to copolymerize propylene and the C₂-C₂₀α-olefin (except propylene) in the presence of the metallocene catalyst,as described below.

As propylene/α-olefin random copolymer (B5) characterized as above,propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B5-1) below issuitably used.

Propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B5-1) is describedin detail below.

In propylene/ethylene/α-olefin random copolymer (B5-1), the content ofpropylene-derived structural units is 55 to 85 mol %, preferably 61 to82 mol %, and more preferably 66 to 75 mol %; the content ofethylene-derived structural units is 5 to 15 mol %, preferably 8 to 14mol %, and more preferably 10 to 14 mol %; and the content of C₄-C₂₀α-olefin-derived structural units (a5) is 0 to 30 mol %, preferably 10to 25 mol %, and more preferably 15 to 20 mol %, wherein the total ofpropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀ α-olefin-derived structural units is 100 mol %.

Propylene/ethylene/α-olefin random copolymer (B5-1) containing propyleneunits, ethylene units, and optionally C₄-C₂₀ α-olefin units in the aboveratio has excellent compatibility with isotactic polypropylene (A5) andprovides propylene-based polymer composition (X5) likely to be excellentin transparency, mechanical strength (strength at break), flexibility,heat resistance, scratch resistance, and compression set resistance.

For example, use of propylene/ethylene/α-olefin random copolymer (B5-1)provides propylene-based polymer composition (X5) with a greatlyimproved elongation when the yield stress is attained in tensile test(YS) (elongation at yield). As a result, the sheet related to the fifthaspect exhibits greatly improved folding properties including thewhitening resistance on folding and wrinkle resistance.

Further, propylene/ethylene/α-olefin random copolymer (B5-1) providespropylene-based polymer composition (X5) with excellent compression setresistance, reducing the permanent deformation caused by folding orcompression of the sheet related to the fifth aspect.

Propylene/ethylene/α-olefin random copolymer (B5-1) preferably has thesame properties as propylene/ethylene/α-olefin copolymer (B1) of thefirst aspect concerning intrinsic viscosity [n], stress at 100%elongation (M100), crystallinity, and glass transition temperature Tg.The effects of these properties are also the same.

When propylene/ethylene/α-olefin random copolymer (B5-1) exhibits amelting point (Tm in ° C.) in the endothermic curve obtained with adifferential scanning calorimeter (DSC), the melting endothermic entalpyΔH is generally 30 J/g or less, and the C₃ content (mol %) and ΔH (J/g)also satisfy the same relation as that for propylene/ethylene/α-olefincopolymer (B1) used in the first aspect.

In propylene/ethylene/α-olefin random copolymer (B5-1), the desiredmolecular weight distribution (Mw/Mn, relative to polystyrene standards,Mw: weight-average molecular weight, Mn: number-average molecularweight) is generally 1.5 to 4.0, preferably 1.5 to 3.0, and morepreferably 1.5 to 2.5 as measured by gel permeation chromatography(GPC).

In the fifth aspect, the triad tacticity (mm-fraction) determined by¹³C-NMR is generally 85% to 97.5%, preferably 87% to 97%, and morepreferably 90% to 97%. With the copolymer having the above range ofmm-fraction, excellent permanent compression set particularly at hightemperature and mechanical strength are attained, which is desirable forthe fifth aspect. The mm-fraction can be determined by the methoddescribed in WO 04/087775 pamphlet from Page 21 line 7 to Page 26 line6.

Propylene/ethylene/α-olefin random copolymer (B5-1) may be produced witha metallocene catalyst used for producing isotactic polypropylene (A5)in a similar manner or with another metallocene catalysts, although themethod is not limited thereto.

<Soft Polymer (C5)>

Soft polymer (C5) optionally used in the fifth aspect is different frompropylene-based polymer (B5) and at least one soft polymer having aShore A hardness of 95 or less and/or a Shore D hardness of 60 or less.Here, Shore A hardness is determined in accordance with JIS K6301, andShore D hardness is determined in accordance with ASTM D-2240.

Soft polymer (C5) is preferably a copolymer in which the content ofethylene-derived structural units is more than 60 mol %, preferably 61mol % or more, and more preferably 61 to 99 mol % of the wholestructural units.

Specific examples of soft polymer (C5) include styrene-based elastomer,ethylene/α-olefin random copolymer, ethylene/vinyl acetate copolymer,ethylene/acrylic acid copolymer, ethylene/methyl methacrylate copolymer,and others. Styrene-based elastomer (C5-1) and ethylene/α-olefincopolymer (C5-2) below are preferably employed.

Specific examples of styrene-based elastomer (C5-1) include the sameelastomers as styrene-based elastomer (C3-1) used in the third aspect,and publicly known such elastomers may be used without limitation.Styrene-based elastomer (C5-1) may be used alone or in combination oftwo or more.

Publicly known paraffin oils with properties as mentioned in the thirdaspect can be incorporated into styrene-based elastomer (C5-1). Blendingsuch paraffin oil largely improves the flexibility of the resultingmolded articles. The amount of paraffin oil blended is preferably 10 to150 parts by weight relative to 100 parts by weight of styrene-basedelastomer (C5-1).

Ethylene/α-olefin random copolymer (C5-2) refers to a copolymer ofethylene and a C₃-C₂₀ α-olefin, preferably a C₃-C₁₀ α-olefin. Preferablyit has the same properties as ethylene/α-olefin random copolymer (C3-2)used in the third aspect concerning density, MFR, and crystallinity.

Specific examples of the C₃-C₂₀ α-olefins used as the co-monomer includeco-monomers like those for ethylene/α-olefin random copolymer (C3-2),and the preferred range is also the same. These co-monomers may be usedalone or in combination of two or more.

The α-olefin content of copolymer (C5-2) is, for example, generally 3mol % or more and less than 40 mol %, preferably 3 to 39 mol %, morepreferably 5 to 30 mol %, and still more preferably 5 to 25 mol %.

If necessary, there may be used a small amount of (an) otherco-monomer(s), for example, a diene such as 1,6-hexadiene and1,8-octadiene, a cycloolefin such as cyclopentene, or the like.

The molecular structure of copolymer (C5-2) may be linear or branchedwith long or short side-chains. Furthermore, a plurality of differentethylene/α-olefin random copolymers may be used as a mixture.

The methods for producing such ethylene/α-olefin random copolymer (C5-2)are not particularly limited to, but include methods similar to thosefor producing ethylene/α-olefin random copolymer used in the thirdaspect. In particular, the copolymer produced using a metallocenecatalyst has a molecular weight distribution (Mw/Mn) of generally 3 orless, and is suitably used in the fifth aspect.

<Propylene-Based Resin Composition (X5)>

Propylene-based resin composition (X5) related to the fifth aspectcomprises isotactic polypropylene (A5) and propylene-based polymer (B5).

Propylene-based resin composition (X5) may further contain soft polymer(C5) and also may contain, as necessary, inorganic filler, additives, orothers below.

In propylene-based polymer composition (X5), isotactic polypropylene(A5) is used in a ratio of 10 to 99 parts by weight, preferably 15 to 98parts by weight, and more preferably 60 to 95 parts by weight, in 100parts by weight of the total of (A5) and (B5). This range is preferredbecause such composition has good moldability and provides sheets withexcellent heat resistance.

In propylene-based polymer composition (X5), propylene-based polymer(B5) is used in a ratio of 1 to 90 parts by weight, preferably 2 to 85parts by weight, and more preferably 5 to 40 parts by weight, in 100parts by weight of the total of (A5) and (B5). Blending in this range ispreferred, because flexibility, mechanical strength, scratch resistance,transparency, and heat resistance are improved and excellent whiteningresistance on folding and wrinkle resistance can be attained.

It is desirable that propylene-based resin composition (X5) contain softpolymer (C5), which is optionally used, in an amount of generally 1 to80 parts by weight and preferably 5 to 70 parts by weight relative to100 parts by weight of the total of (A5) and (B5). The compositioncontaining such amount of soft polymer (C5) can provide molded articleswith excellent flexibility, surface hardness, and impact resistance, andin particular, excellent low-temperature impact strength.

Propylene-based resin composition (X5) may further contain, asnecessary, other resins, other rubbers, inorganic filler, additives, andothers as long as the objectives of the fifth aspect are not impaired.

The inorganic fillers used in the fifth aspect include, for example,talc, clay, calcium carbonate, mica, silicates, carbonates, and glassfibers. Among these, talc and calcium carbonate are preferable, and talcis particularly preferable. It is desirable that talc has an averageparticle diameter of 1 to 5 μm and preferably 1 to 3 μm. The inorganicfillers may be used alone or in combination of two or more.

Propylene-based polymer composition (X5) may further contain additivessuch as weathering stabilizers, heat stabilizers, antistatic agents,anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants,pigments, dyes, plasticizers, anti-aging agents, hydrochloric acidabsorbers, antioxidants, and nucleating agents, as long as theobjectives of the fifth aspect are not impaired.

The amount of other resins, other rubbers, inorganic filler, additives,and others described above is not particularly limited as long as theobjects of the first aspect are not impaired. In an embodiment, thetotal of isotactic polypropylene (A5), propylene-based polymer (B5),and, if any, soft polymer (C5) is 60 wt % or more and preferably 80 wt %to 100 wt % of the whole composition, and the remainder is accounted forby the above described other resins, other rubbers, inorganic filler,additives, and others.

Propylene-based polymer composition (X5) can be produced usingindividual components in the above ranges of content by various publiclyknown methods, for example, multi-step polymerization; a method ofmixing the components with a Henschel mixer, a V-blender, a ribbonblender, a tumbler blender, or the like; and a method of mixing thecomponents followed by melt-kneading with a single-screw or twin-screwextruder, a kneader, a Banbury mixer, or the like and subsequentgranulation or pulverization.

Propylene-based polymer composition (X5) may also be obtained by addinga small amount of isotactic polypropylene (A5) to propylene-basedpolymer (B5) to prepare pellets in advance, followed by further addingisotactic polypropylene (A5) to the pellets. In this case, other resins,other rubbers, inorganic filler, additives, and others as well as softpolymer (C5) may be added on the pelletization or may be added whenisotactic polypropylene (A5) is further added after the pelletization.

When propylene-based polymer composition (X5) does not contain the abovestyrene-based elastomer, but contains a softener, the amount of softenerto be added is not particularly limited, but in one preferredembodiment, it is 15 parts by weight or less and preferably 10 parts byweight relative to 100 parts by weight of the total of isotacticpolypropylene (A5), propylene-based polymer (B5), and if any, softpolymer (C5). An embodiment containing no softener is also preferred.

<Polyolefin Decorative Sheet>

The polyolefin decorative sheet of the fifth aspect is used in publiclyknown decorative boards wherein said sheet is laminated on the surfaceof adherants such as plywood, steel plate, aluminum plate, particleboard, MDF (medium-density fiberboard), inorganic board (gypsum board,etc.), concrete wall, plastic board, foam, and heat insulator, with anadhesive or otherwise. The propylen decorative sheets of the fifthaspect also include building material-protective sheets, for example, asheet used as a surface layer of floors, walls, ceilings, and otherparts. Both decorative and protective sheets are used to produce pictureor print designs and to protect surfaces.

A typical example of the polyolefin decorative sheet related to thefifth aspect is, for example, a propylen decorative sheet having atleast one component layer made of propylene-based polymer composition(X5) as shown in FIG. 5-1. The decorative sheet may contain two or morelayers made of propylene-based polymer composition (X5). In this case,these two or more layers may be composed of the same components ordifferent components from each other.

The polyolefin decorative sheet of the fifth aspect may contain, besidesthe layer(s) made of propylene-based polymer composition (X5), publiclyknown component layers of decorative sheets, such as a print or picturelayer displaying designs, a surface-coating layer, a luster-adjustinglayer, a shielding layer (which prevents the substrate surface frombeing seen through the foreground layer and may also serves as a basematerial), and an adhesive layer bonding these layers together.

The configurations of the decorative sheet related to the fifth aspectis not particularly limited, but include such configurations asdescribed in the first aspect.

Namely, the configurations of the decorative sheet related to the fifthaspect are not particularly limited, but include, for example, anembodiment wherein the decorative sheet contains a layer [a] made ofpropylene-based polymer composition (X5), at least one layer [b]selected from print layer, picture layer, and shielding layer, and ifnecessary at least one layer [c] selected from surface-coating layer andluster-adjusting layer.

In another embodiment, the decorative sheet contains a shielding layer[d], a layer [a] made of propylene-based polymer composition (X5), atleast one layer [b] selected from print layer and picture layer, and ifnecessary at least one layer [c] selected from surface-coating layer andluster-adjusting layer.

Since the layer made of propylene-based polymer composition (X5) isexcellent in strength at break, scratch resistance, abrasion resistance,whitening resistance on folding, wrinkle resistance, heat resistance,and transparency, it is suitably used as a protective layer for a printor picture layer (that is, the layer made of propylene-based polymercomposition (X5) is used as a surface layer protecting a print orpicture layer, and onto the layer of the polymer composition there maybe applied publicly known treatment such as providing a surface-coatinglayer or a luster-adjusting layer as long as the objectives of the fifthaspect are not impaired). The polyolefin decorative sheets with suchconfiguration are particularly preferable.

The layer made of propylene-based polymer composition (X5) is alsosuitably used as one layer in combination with a layer made of anothercomponent because of its excellent flexibility and water resistance. Inthis case, the layer made of propylene-based polymer composition (X5)can be bonded without a publicly known adhesive or an adhesive havingthe same effect with the publicly known adhesive. Specifically,sufficient bonding strength can be attained by publicly known hot-meltbondings such as heat lamination, extrusion lamination, sandwichlamination, and co-extrusion.

Therefore, as shown in FIG. 5-2, the layer made of propylene-basedpolymer composition (X5) can be suitably used for a polyolefindecorative sheet in combination with layers made of a polyolefin resincomposition other than propylene-based resin composition (X5), that is,polyolefin resin composition out of the scope of propylene-based resincomposition (X5) (including publicly known adhesive polyolefin resinlayers). Namely, the polyolefin decorative sheet of the fifth aspectpreferably contains at least one additional component layer made of apolyolefin resin composition other than propylene-based polymercomposition (X5).

The polyolefin decorative sheet of the fifth aspect is excellent inwrinkle resistance on folding. In particular, when the layer made ofpropylene-based polymer composition (X5) is laminated with the layermade of a polyolefin resin composition other than propylene-basedpolymer composition (X5), the wrinkle resistance is excellent.

The polyolefin decorative sheet is suitably used, even though the sheethas been formed by laminating, without any adhesive, the back surface ofthe layer made of propylene-based polymer composition (X5) and the layermade of a polyolefin resin composition other than propylene-basedpolymer composition (X5). Here, “lamination without any adhesive” meansdirect lamination by hot-melt bonding.

As the polyolefin resin composition other than propylene-based polymercomposition (X5), any composition other than propylene-based polymercomposition (X5), that is, polyolefin resin composition out of the scopeof propylene-based polymer composition (X5) may be used withoutparticular limitation. Specifically, the polyolefin resin compositionsinclude polyethylene, polypropylene, poly-α-olefin, ethylene/α-olefincopolymer, ethylene/polar vinyl monomer copolymer, and resincompositions containing two or more of these.

The above polyolefin resin composition may further contain additivessuch as inorganic filler, weathering stabilizers, heat stabilizers,antistatic agents, anti-slip agents, anti-blocking agents, anti-foggingagents, lubricants, pigments, dyes, plasticizers, anti-aging agents,hydrochloric acid absorbers, antioxidants, and nucleating agents, aslong as the objectives of the fifth aspect are not impaired.

The thickness of the layer made of propylene-based polymer composition(X5) is, although not particularly limited to, generally 5 to 2000 μm.

To the polyolefin decorative sheet of the fifth aspect, there may beapplied publicly known processing such as embossing, engraining, andwiping.

For producing the polyolefin decorative sheet of the fifth aspect, anypublicly known method may be employed without particular limitation.

The applications of the polyolefin decorative sheet are, although notparticularly limited to, preferably the same as those of the firstaspect.

Namely, the applications of the polyolefin decorative sheet are notparticularly limited, and the sheet is preferably used for home electricappliances and furniture such as TV cabinets, stereo-speaker boxes,video cabinets, various storage furniture, and unified furniture;housing members such as doors, door frames, window sashes, crowns,plinth, and opening frames; furniture members such as doors of kitchenor storage furniture; building materials such as flooring material,ceiling material, and wall paper; automobile interior materials;stationery; office goods; and others.

6. Sixth Aspect

Hereinafter, the sixth aspect of the present invention is explained indetail.

<Propylene-Based Polymer (A6)>

Propylene-based polymers (A6) used in the sixth aspect includehomopolypropylene and copolymers of propylene and at least oneC₂-C₂₀α-olefin except propylene. The C₂-C₂₀α-olefins except propyleneinclude α-olefins like those for isotactic polypropylene (A1) used inthe first aspect. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

The structural units derived from these α-olefins may be contained in anamount of 35 mol % or less and preferably 30 mol % or less of the wholeunits composing propylene-based polymer (A6).

The melt flow rate (MFR) of propylene-based polymer (A6) is generally0.01 to 1000 g/10 min, preferably 0.05 to 100 g/10 min, and morepreferably 0.1 to 50 g/10 min as measured at 230° C. under a load of2.16 kg in accordance with ASTM D1238.

The melting point of propylene-based polymer (A6) measured with adifferential scanning calorimeter (DSC) is generally 120° C. or higher,preferably 120 to 170° C., and more preferably 125 to 165° C.

Propylene-based polymer (A6) may be either isotactic or syndiotactic,but preferably isotactic considering heat resistance and others.

There may be used, if necessary, two or more kinds of propylene-basedpolymers (A6) together, for example, two or more components different inmelting point or rigidity.

For attaining the desired properties, there may be used, aspropylene-based polymer (A6), one or more polymers selected fromhomopolypropylene with excellent heat resistance (publicly known,generally containing 3 mol % or less of comonomer except propylene),block polypropylene with excellent balance of heat resistance and impactresistance (publicly known, generally containing from 3 to 30 wt % ofn-decane-soluble rubber components), and random polypropylene withexcellent balance of flexibility and transparency (publicly known,generally having a melting peak of 120° C. or higher and preferably 125°C. to 150° C. as measured with a differential scanning calorimeter(DSC)).

Such propylene-based polymer (A6) can be produced by methods like thosefor producing isotactic polypropylene (A1) used in the first aspect.

<Propylene-Based Polymer (B6)>

Propylene-based polymers (B6) used in the six embodiment includehomopolypropylene and copolymers of propylene and at least oneC₂-C₂₀α-olefin except propylene. The C₂-C₂₀α-olefins except propyleneinclude α-olefins like those used for propylene-based polymer (A6).Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

In propylene-based polymer (B6), the content of propylene-derivedstructural units is generally 40 to 100 mol %, preferably 40 to 99 mol%, more preferably 40 to 92 mol %, and still more preferably 50 to 90mol %; and the content of structural units derived from a C₂-C₂₀α-olefin (except propylene) used as a co-monomer is generally 0 to 60mol %, preferably 1 to 60 mol %, more preferably 8 to 60 mol %, andstill more preferably 10 to 50 mol %, wherein the total of propyleneunits and C₂-C₂₀ α-olefin units is 100 mol %.

Propylene-based polymer (B6) generally has a melt flow rate (MFR,measured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238) of 0.1 to 50 (g/10 min).

The melting point of propylene-based polymer (B6) is lower than 120° C.or not observed, and preferably 100° C. or lower or not observed, asmeasured with a differential scanning calorimeter (DSC). Here, “meltingpoint is not observed” means that any melting endothermic peak ofcrystal having a melting endothermic entalpy of crystal of 1 J/g or moreis not observed in the temperature range of −150 to 200° C. Themeasurement conditions are as described in Examples of the sixth aspect.

In propylene-based polymer (B6), the intrinsic viscosity [η] measured indecalin at 135° C. is generally 0.01 to 10 dl/g and preferably 0.05 to10 dl/g.

Propylene-based polymer (B6) preferably has the same triad tacticity(mm-fraction) as that of propylene/ethylene/α-olefin copolymer (B1) ofthe first aspect, whereby the same effect can be obtained.

Namely, the triad tacticity (mm-fraction) of propylene-based polymer(B6) determined by ¹³C-NMR is preferably 85% or more, more preferably85% to 97.5%, still more preferably 87% to 97%, and particularlypreferably 90% to 97%. With the above range of triad tacticity(mm-fraction), the balance of flexibility and mechanical strength isparticularly excellent, which is desirable for the sixth aspect. Themm-fraction can be determined by the method described in WO 04/087775pamphlet from Page 21 line 7 to Page 26 line 6.

The methods for producing propylene-based polymer (B6), although notparticularly limited to, include a method similar to that for producingpropylene-based polymer (B5) used in the fifth aspect.

Specific examples of propylene/α-olefin random copolymer (B6) with theabove properties include propylene/C₄-C₂₀ α-olefin random copolymer(B6-1) and propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2).

When the propylene-based resin composition contains propylene/C₄-C₂₀α-olefin random copolymer (B6-1), which is compatible with crystallinepolypropylene components, the composition has more excellent mechanicalstrength, elongation at break, scratch resistance, and whiteningresistance.

Propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2) is alsocompatible with crystalline polypropylene components, aspropylene/C₄-C₂₀ α-olefin random copolymer (B6-1), so that thepropylene-based resin composition containing propylene/ethylene/C₄-C₂₀α-olefin random copolymer (B6-2) has more excellent flexibility, scratchresistance, and whitening resistance.

Details are explained below on propylene/C₄-C₂₀ α-olefin randomcopolymer (B6-1) and propylene/ethylene/C₄-C₂₀ α-olefin random copolymer(B6-2) suitably used in the sixth aspect.

[Propylene/C₄-C₂₀ α-Olefin Random Copolymer (B6-1)]

Propylene/C₄-C₂₀ α-olefin random copolymer (B6-1) preferably used in thesixth aspect has properties (a) and (b) below:

(a) the molecular weight distribution (Mw/Mn) measured by gel permeationchromatography (GPC) is 1 to 3; and

(b) the melting point Tm (° C.) and the comonomer content M (mol %)determined by ¹³C-NMR spectrum satisfy the relation,

146exp(−0.022 M)≧Tm≧125exp(−0.032 M),

wherein Tm is lower than 120° C., preferably lower than 100° C.

The melting point Tm of propylene/C₄-C₂₀ α-olefin random copolymer(B6-1) is measured with a DSC as follows: a sample put in an aluminumpan is heated to 200° C. at 100° C./min, kept at 200° C. for 5 min,cooled to −150° C. at 10° C./min, and heated to 200° C. at 10° C./min,wherein the temperature when an endothermic peak is observed in thesecond heating step is counted as the melting point Tm. The meltingpoint Tm is generally lower than 120° C., preferably lower than 100° C.,more preferably 40 to 95° C., still more preferably 50 to 90° C. Withthe above range of melting point Tm, the composition provides moldedarticles with excellent balance between flexibility and mechanicalstrength in particular. Furthermore, because of reduced surfacestickiness, the molded articles of the composition related to the sixthaspect have an advantage of good processability.

Desirably, propylene/C₄-C₂₀ α-olefin random copolymer (B6-1) furthersatisfies that,

(c) the crystallinity measured by X-ray diffractometry is preferably 40%or less, and more preferably 35% or less.

In propylene/C₄-C₂₀ α-olefin random copolymer (B6-1), the content ofC₄-C₂₀ α-olefin-derived structural units is preferably 5 to 50 mol %,and more preferably 10 to 35 mol %. Particularly, 1-butene is preferablyused as the C₄-C₂₀ α-olefin.

Such propylene-based polymer (B6-1) is produced by methods similar tothose for producing soft propylene/α-olefin random copolymer (B3) usedin the third aspect. For example, the method described in WO 04/087775pamphlet may be employed. [Propylene/ethylene/C₄-C₂₀ α-olefin randomcopolymer (B6-2)]

Propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2) preferablyused in the sixth aspect has properties (m) and (n) below:

(m) the molecular weight distribution (Mw/Mn) measured by gel permeationchromatography (GPC) is 1 to 3; and

(n) the content of propylene-derived structural units is 40 to 85 mol %,the content of ethylene-derived structural units is 5 to 30 mol %, andthe content of C₄-C₂₀ α-olefin-derived structural units is 5 to 30 mol%, wherein the total of propylene-derived structural units,ethylene-derived structural units, and C₄-C₂₀ α-olefin-derivedstructural units is 100 mol %; and the total of ethylene-derivedstructural units and C₄-C₂₀ α-olefin-derived structural units preferablyis 60 to 15 mol %.

It is preferred that propylene/ethylene/C₄-C₂₀ α-olefin random copolymer(B6-2) further satisfies at least one or more, more preferably both, ofproperties (o) and (p) below:

(o) the Shore hardness A is 30 to 80, and preferably 35 to 60; and

-   -   (p) the crystallinity measured with X-ray diffractometry is 20%        or less, and preferably 10% or less.

The melting point, Tm, of propylene/ethylene/C₄-C₂₀ α-olefin randomcopolymer (B6-2) is preferably not higher than 50° C. or not observed,and more preferably not observed, when measured with a DSC. The meltingpoint can be measured by the same way as the case of copolymer (B6-1)described above.

For the contents of propylene and other co-monomer components, morespecifically, the content of propylene-derived structural units ispreferably 60 to 82 mol % and more preferably 61 to 75 mol %, thecontent of ethylene-derived structural units is preferably 8 to 15 mol %and more preferably 10 to 14 mol %, and the content of C₄-C₂₀α-olefin-derived structural units is preferably 10 to 25 mol % and morepreferably 15 to 25 mol %. Particularly, 1-butene is preferably used asthe C₄-C₂₀ α-olefin.

Such propylene/ethylene/α-olefin random copolymer (B6-2) can be producedby methods similar to those for producing soft propylene/α-olefin randomcopolymer (B3) used in the third aspect, for example, by the methoddescribed in WO 04/087775 pamphlet.

When propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2) is usedin the sixth aspect, molded articles obtained have more improvedflexibility and excellent low-temperature embrittlement property. Forexample, when the molded article is an electrical wire, it has anadvantage that its electrical wire cover is resistant to cracking at lowtemperature.

<Elastomer (C6)>

Elastomer (C6) used in the sixth aspect is one or more elastomerselected from ethylene-based elastomer (C6-1) containing 61 mol % ormore of ethylene-derived structural units in the whole structural units,and styrene-based elastomer (C6-2) containing 5 to 70 wt % ofstyrene-derived structural units in the whole structural units.

Elastomer (C6) is not particularly limited as long as its Shore Ahardness is in the range of 30 to 90. The elastomers include, forexample, styrene/butadiene rubber and its hydrogenated derivative,ethylene/α-olefin random copolymer, ethylene/vinyl acetate copolymer,ethylene/acrylic acid copolymer, ethylene/methyl methacrylate copolymer,and others.

As ethylene-based elastomer (C6-1), ethylene/α-olefin random copolymer(C6-1-1) is preferably used. Ethylene/α-olefin random copolymer (C6-1-1)refers to a copolymer of ethylene and a C₃-C₂₀ α-olefin, preferably aC₃-C₁₀ α-olefin, and preferably has the same properties asethylene/α-olefin random copolymer (C3-2) used in the third aspectconcerning density, MFR, and crystallinity.

Specific examples of the C₃-C₂₀ α-olefins used as a co-monomer includeco-monomers like those for ethylene/α-olefin random copolymer (C3-2)used in the third aspect. The preferable range is also the same. Thesemay be used alone or in combination of two or more.

The α-olefin content in copolymer (C6-1-1) is, for example, generally 3to 39 mol %, preferably 5 to 30 mol %, and more preferably 5 to 25 mol%.

There may be contained, if necessary, a small amount of structural unitsderived from another co-monomer, for example, a diene such as1,6-hexadiene and 1,8-octadiene, a cycloolefin such as cyclopentene, orothers.

The molecular structure of copolymer (C6-1-1) may be linear or branchedwith long or short side-chains.

A plurality of different ethylene/α-olefin random copolymers (C6-1-1)may be used as a mixture.

The methods for producing such ethylene/α-olefin random copolymer(C6-1-1) is not particularly limited to, but include the same methods asthose for producing ethylene/α-olefin random copolymer (C3-2) used inthe third aspect. In particular, the copolymer produced with ametallocene catalyst has a molecular weight distribution of generally 3or less, and is preferably used in the sixth aspect.

Specific examples of styrene-based elastomer (C6-2) include the sameelastomers as styrene-based elastomer (C3-1) used in the third aspect,and publicly known elastomers may be used without limitation.Styrene-based elastomer (C6-2) may be used alone or in combination oftwo or more.

In the sixth aspect, ethylene elastomer (C6-1) and styrene-basedelastomer (C6-2) may be used together.

<Inorganic Filler (D6)>

As inorganic filler (D6) used in the sixth aspect, there may be usedvarious substances, for example, metal compounds, inorganic compoundssuch as glass, ceramics, talc, and mica, or others. Among them, metalhydroxides, metal carbonates (carbonated compounds), and metal oxidesare preferably used. Inorganic filler (D6) may be used alone or incombination of two or more.

The average particle diameter of inorganic filler (D6) is generally 0.1to 20 μm, and preferably 0.5 to 15 μm, which is determined with thelaser method.

Inorganic filler (D6) may be surface-treated with a fatty acid such asstearic acid and oleic acid, an organosilane, or others. In theinorganic filler, fine particles with the above average particlediameter may be agglomerated.

<Oil (E6)>

Oils (E6) used in the sixth aspect include various oils such as paraffinoil, naphthene oil, aromatic oil, and silicone oil. Among them, paraffinoil and naphthene oil are preferably used.

Oil (E6), although not particularly limited, preferably has a kinematicviscosity at 40° C. of generally 20 to 800 cSt (centiStrokes), andpreferably 40 to 600 cSt. For oil (E6), it is desirable that the pourpoint is generally 0 to −40° C., and preferably 0 to −30° C., while theflash point (COC test) is generally 200 to 400° C., and preferably 250to 350° C. When oil (E6) is blended, the propylene-based resincomposition of the sixth aspect is particularly excellent inlow-temperature properties such as cold embrittlement resistance andscratch resistance.

The naphthene process oil suitably used for the sixth aspect is apetroleum-derived softener containing 30 to 45 wt % of naphthenehydrocarbons, which is blended in rubber processing for the purpose ofsoftening, dispersing blended components, lubrication, improvinglow-temperature properties, or others. When such process oil is blended,the resin composition has further improved pour point on molding, and inmolded articles thereof, the flexibility and low-temperature propertiesare further improved and the surface stickiness caused by bleeding issuppressed. In the sixth aspect, a naphthene process oil having anaromatic hydrocarbon content of 10 wt % or less is preferably used. Whenthe composition contains such naphthene oil, the surface bleeding issuppressed in molded articles, although the reason is unclear.

<Graft-Modified Polymer (E6)>

The starting polymers for graft-modified polymer (E6) include, forexample, polymers of one or more α-olefin, styrene-based blockcopolymers, and others. In particular, ethylene-based polymers,propylene-based polymers, and styrene-based block copolymers arepreferable. The above α-olefins include, for example, C₂-C₂₀ α-olefins.

The ethylene-based polymer is preferably polyethylene or anethylene/α-olefin copolymer. Among ethylene/α-olefin copolymersdescribed above, ethylene/C₃-C₁₀ α-olefins copolymers are preferable.The C₃-C₁₀ α-olefins include, specifically, propylene, 1-butene,1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene,3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 1-octene, 3-ethyl-1-hexene,1-octene, 1-decene, and others. These may be used alone or incombination of two or more. Above all, at least one selected frompropylene, 1-butene, 1-hexene, and 1-octene is desirably used.

For the content of each structural units in the ethylene-basedcopolymer, it is desirable that the content of ethylene-derivedstructural units is 75 to 95 mol %, and the content of structural unitsderived from at least one compound selected from C₃-C₁₀ α-olefins is 5to 20 mol %.

The ethylene/α-olefin copolymer preferably satisfies:

(i) the density is 0.855 to 0.910 g/cm³, and preferably 0.857 to 0.890g/cm³;

(ii) the melt flow rate (MFR, at 190° C. under a load of 2.16 kg) is inthe range of 0.1 to 100 g/10 min, and preferably 0.1 to 20 g/10 min;

(iii) the index of molecular weight distribution (Mw/Mn) determined byGPC is 1.5 to 3.5, preferably 1.5 to 3.0, and more preferably 1.8 to2.5; and

-   -   (iv) the B-value determined from ¹³C-NMR spectrum using the        following equation is 0.9 to 1.5, and preferably 1.0 to 1.2.

B-value=[POE]/(2·[PE][PO])

(In the formula, [PE] denotes the mole fraction of ethylene-derivedstructural units in the copolymer; [PO] denotes the mole fraction ofα-olefin-derived structural units in the copolymer; and [POE] is theratio of the number of ethylene-α-olefin dyads to the total number ofdyads in the copolymer.)

Besides the above, it is desirable that the ethylene/α-olefin copolymerhas the same properties as those of the ethylene/α-olefin copolymer usedfor component (A6). For this copolymer, the co-monomer species, density,and molecular weight may be identical to or different from those forcomponent (A6).

The graft-modified polymer used in the sixth aspect can be obtained by,for example, graft-modification of a poly-α-olefin, a styrene-basedblock copolymer, or the like with a polar group-containing vinylcompound. The vinyl compounds include vinyl compounds having anoxygen-containing group such as acid, acid anhydride, ester, alcohol,epoxy, and ether, vinyl compounds having a nitrogen-containing groupsuch as isocyanate and amide, and vinyl compounds having asilicon-containing group such as vinylsilane.

Among them, the vinyl compound having an oxygen-containing group ispreferable. Specifically, unsaturated epoxy monomers, unsaturatedcarboxylic acids, and their derivatives are preferable.

The unsaturated epoxy monomers include unsaturated glycidyl ethers, andunsaturated glycidyl esters (for example, glycidyl methacrylate).

The unsaturated carboxylic acids include acrylic acid, maleic acid,fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,crotonic acid, isocrotonic acid, and nadic acid (TM,endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid).

The unsaturated carboxylic acid derivatives include acid halide, amide,imide, anhydride, and ester of the unsaturated carboxylic acids.Specifically, they include maleyl chloride, maleimide, maleic anhydride,citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidylmaleate, and others.

The unsaturated dicarboxylic acids and their anhydrides are morepreferable among them, particularly maleic acid, nadic Acid™, and theiranhydrides are preferably used.

Such unsaturated carboxylic acid or its derivative may bond to anycarbon atom in the unmodified ethylene-based copolymer withoutparticular limitation on the position to be grafted.

Graft-modified polymer (F6) described above is prepared by various knownmethods, for example, by the followings:

(1) To the unmodified polymer melted with an extruder or the like, theunsaturated carboxylic acid or the like is added to begraft-copolymerized; or

(2) To a solution prepared by dissolving the unmodified polymer in asolvent, the unsaturated carboxylic acid or the like is added to begraft-copolymerized.

In either method, it is preferred that the reaction is conducted in thepresence of a radical initiator for efficient graft-copolymerization ofthe above grafting monomer such as unsaturated carboxylic acids.

The radical initiators used herein include, for example, organicperoxides, azo compounds, and others.

The organic peroxides include benzoyl peroxide, dichlorobenzoylperoxide, dicumyl peroxide, and others.

The azo compounds include azobisisobutyronitrile, dimethylazoisobutyrate, and others.

Specifically, the radical initiators suitably used are dialkyl peroxidessuch as dicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and1,4-bis(tert-butylperoxyisopropyl)benzene.

The amount of radical initiator to be used is generally 0.001 to 1 partby weight, preferably 0.003 to 0.5 parts by weight, and more preferably0.05 to 0.3 parts by weight, relative to 100 parts by weight of theunmodified polymer.

In the graft-polymerization with or without the above radical initiator,the reaction temperature is generally 60 to 350° C., and preferably 150to 300° C.

In graft-modified polymer (F6) thus obtained, the ratio of polargroup-containing vinyl compound grafted is generally 0.01 to 10 wt %,and preferably 0.05 to 5 wt %, wherein the weight of graft-modifiedpolymer is 100 wt %. In the sixth aspect, use of graft-modified polymer(F6) particularly enhances interactions of the inorganic filler with thepropylene-based polymer, propylene/α-olefin random copolymer, andelastomer;

therefore, the composition provides molded articles with excellentbalance of tensile strength and scratch resistance.

<Propylene-Based Resin Composition (X6) and Molded Article>

Propylene-based resin composition (X6) of the sixth aspect of thepresent invention contains 0 to 80 wt % of propylene-based polymer (A6),5 to 85 wt % of propylene-based polymer (B6), 0 to 40 wt % of elastomer(C6), and 15 to 80 wt % of inorganic filler (D6), wherein the total ofcomponents (A6), (B6), (C6), and (D6) is 100 wt %.

When propylene/C₄-C₂₀α-olefin random copolymer (B6-1) is used aspropylene-based polymer (B6), it is desirable that propylene-based resincomposition (X6) contains propylene-based polymer (A6) in an amount of 0to 80 wt %, preferably 0 to 70 wt %, more preferably 0 to 60 wt %, stillmore preferably 0 to 50 wt %, and particularly preferably 10 to 40 wt %;propylene/C₄-C₂₀ α-olefin random copolymer (B6-1) in an amount of 5 to85 wt %, preferably 10 to 80 wt %, more preferably 10 to 70 wt %, stillmore preferably 15 to 60 wt %, and particularly preferably 25 to 55 wt%; elastomer (C6) in an amount of 0 to 40 wt %, preferably 0 to 30 wt %,more preferably 0 to 25 wt %, still more preferably 5 to 20 wt %, andparticularly preferably 5 to 15 wt %; and inorganic filler (D6) in anamount of 15 to 80 wt %, preferably 20 to 70 wt %, more preferably 30 to70 wt %, still more preferably 30 to 60 wt %, and particularlypreferably 35 to 60 wt %, wherein the total of components (A6), (B6),(C6), and (D6) is 100 wt %.

When propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2) is usedas propylene-based polymer (B6), it is desirable that propylene-basedresin composition (X6) contains propylene-based polymer (A6) in anamount of 0 to 80 wt %, preferably 0 to 70 wt %, more preferably 0 to 60wt %, still more preferably 0 to 50 wt %, and particularly preferably 10to 40 wt %; propylene/1-butene random copolymer as (B6-2) in an amountof 5 to 85 wt %, preferably 10 to 80 wt %, more preferably 10 to 70 wt%, still more preferably 15 to 50 wt %, and particularly preferably 20to 50 wt %; elastomer (C6) in an amount of 0 to 40 wt %, preferably 0 to30 wt %, more preferably 0 to 25 wt %, still more preferably 5 to 20 wt%, and particularly preferably 5 to 15 wt %; and inorganic filler (D6)in an amount of 15 to 80 wt %, preferably 20 to 70 wt %, more preferably30 to 70 wt %, still more preferably 30 to 60 wt %, and particularlypreferably 35 to 60 wt %, wherein the total of components (A6), (B6),(C6), and (D6) is 100 wt %.

The amount of oil (E6) used in the sixth aspect is 0.1 to 20 parts byweight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to8 parts by weight relative to 100 parts by weight to the total ofcomponents (A6), (B6), (C6), and (D6). When the composition contains oil(E6) in the above range, the effect of improving low-temperatureproperties is remarkable while the oil is seldom bled in surfaces ofmolded articles; hence such composition is preferred.

When both graft-modified polymer (F6) and propylene/C₄-C₂₀ α-olefinrandom copolymer (B6-1) are used, it is desirable that propylene-basedresin composition (X6) contains propylene-based polymer (A6) in anamount of 0 to 80 wt %, preferably 0 to 70 wt %, more preferably 0 to 60wt %, still more preferably 0 to 50 wt %, and particularly preferably 10to 40 wt %; propylene/C₄-C₂₀ α-olefin random copolymer (B6-1) in anamount of 5 to 85 wt %, preferably 5 to 80 wt %, more preferably 5 to 65wt %, still more preferably 5 to 55 wt %, and particularly preferably 5to 45 wt %; elastomer (C6) in an amount of 0 to 40 wt %, preferably 0 to30 wt %, more preferably 0 to 25 wt %, still more preferably 0 to 20 wt%, and particularly preferably 0 to 15 wt %; and inorganic filler (D6)in an amount of 15 to 80 wt %, preferably 20 to 70 wt %, more preferably30 to 70 wt %, still more preferably 30 to 60 wt %, and particularlypreferably 35 to 60 wt %, wherein the total of components (A6), (B6),(C6), and (D6) is 100 wt %. In this case, graft-modified polymer (F6) isadded in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 8parts by weight, relative to 100 parts by weight of the total ofcomponents (A6), (B6), (C6), and (D6). When the composition containsgraft-modified polymer (F6) in the above range, the effect of improvingscratch resistance is remarkable and the composition has excellentflowability; hence such composition is preferred.

When graft-modified polymer (F6) is used and propylene/ethylene/C₄-C₂₀α-olefin random copolymer (B6-2) is used as propylene/α-olefin randomcopolymer (B6), it is desirable that propylene-based resin composition(X6) contains propylene-based polymer (A6) in an amount of 0 to 80 wt %,preferably 0 to 70 wt %, more preferably 0 to 60 wt %, still morepreferably 0 to 50 wt %, and particularly preferably 10 to 40 wt %;propylene/ethylene/C₄-C₂₀ α-olefin random copolymer (B6-2) in an amountof 5 to 85 wt %, preferably 5 to 80 wt %, more preferably 5 to 65 wt %,still more preferably 5 to 50 wt %, and particularly preferably 5 to 40wt %; elastomer (C6) in an amount of 0 to 40 wt %, preferably 0 to 30 wt%, more preferably 0 to 25 wt %, still more preferably 0 to 20 wt %, andparticularly preferably 0 to 15 wt %; and inorganic filler (D6) in anamount of 15 to 80 wt %, preferably 20 to 70 wt %, more preferably 30 to70 wt %, still more preferably 30 to 60 wt %, and particularlypreferably 35 to 60 wt %, wherein the total of components (A6), (B6),(C6), and (D6) is 100 wt %. In this case, the graft-modified polymer(F6) is blended in an amount of generally 0.1 to 30 parts by weight,preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 8parts, by weight relative to 100 parts by weight of the total ofcomponents (A6), (B6), (C6), and (D6). When the composition containsgraft-modified polymer (F6) in the above range, the effect of improvingscratch resistance is remarkable and the composition has excellentflowability; therefore such composition is preferred.

As long as the objectives of the sixth aspect are not impaired,propylene-based resin composition (X6) may further contain other resins,other rubbers, additives such as antioxidants, heat stabilizers,weathering stabilizers, anti-slip agents, anti-blocking agents,nucleating agents, pigments, hydrochloric acid absorbers, and inhibitorsagainst copper-induced damage. Such other resins, other rubbers,additives, and others described above may be added in any amount withoutparticular limitation as long as the objectives of the sixth aspect arenot impaired. In a preferred embodiment, for example, the total of (A6),(B6), (C6), and (D6) is 60 to 100 wt %, and preferably 80 to 100 wt % ofthe whole composition (X6), and the remainder is accounted for by theabove described other resins, other rubbers, additives, oil (E6),graft-modified polymer (F6), and others.

<Method for Producing Propylene-Based Resin Composition (X6)>

Propylene-based resin composition (X6) of the sixth aspect can beproduced by publicly known methods, for example, by melt-kneading of theabove components.

When propylene-based resin composition (X6) contains graft-modifiedpolymer (F6), propylene-based polymer (B6) and graft-modified polymer(F6) are melt-kneaded to produce propylene-based polymer composition(G6), which is subsequently melt-kneaded together with inorganic filler(D6), if necessary propylene-based polymer (A6), and if necessary one ormore elastomers (C6) selected from ethylene-based elastomer (C6-1) andstyrene-based elastomer (C6-2). This process is preferable becausescratch resistance can be further improved while no other properties areimpaired.

Here, part of (B6) or (F6) may be supplied independently ofpropylene-based polymer composition (G6) (melt-kneaded product), similarto component (A6) and others, without preliminarily melt-kneading.However, it is the most effective that whole (B6) and (F6) arepreliminarily melt-kneaded to prepare propylene-based polymercomposition (G6) (melt-kneaded product), and then the composition issupplied.

<Propylene-Based Polymer Composition (G′6)>

Propylene-based polymer composition (G′6) comprises propylene-basedpolymer (B6) and graft-modified polymer (F6). The content of (B6) is 99to 14 parts by weight and that of (F6) is 1 to 86 parts by weight,wherein the total of (B6) and (F6) is 100 parts by weight. Particularlypreferably, the content of (B6) is 99 to 50 parts by weight and that of(F6) is 1 to 50 parts by weight. When propylene-based polymercomposition (G′6) is used for producing propylene-based resincomposition (X6), the ratio of (B6) to (F6) may be selected according tothe ratio of (B6) to (F6) in said propylene-based resin composition(X6). Propylene-based polymer composition (G′6) can be produced, forexample, by melt-kneading (B6) and (F6).

<Molded Article>

The molded article of the sixth aspect is made of propylene-based resincomposition (X6) described above. Molded articles with various shapesare obtained from propylene-based resin composition (X6) usingconventional publicly-known melt-molding methods. The melt-moldingmethods include, for example, extrusion molding, rotation molding,calendar molding, injection molding, compression molding, transfermolding, powder molding, blow molding, vacuum molding, and others. Themolded article may be a composite with a molded article made of anothermaterial, for example, laminate.

The molded articles are suitably used, for example, as coatings forelectrical wire bodies such as electrical wire insulators and wiresheaths. The coating layers, such as electrical wire insulators and wiresheaths, are formed around electrical wire bodies using conventionalpublicly-known methods, for example, extrusion molding.

The electrical wire of the sixth aspect has an insulator made ofpropylene-based resin composition (X6) and/or a sheath made ofpropylene-based resin composition (X6). The electrical wire is, inparticular, preferably an electrical wire for automobiles (automobileelectrical wire) and an electrical wire for apparatuses (insulated wiresfor electric apparatus).

Propylene-based resin composition (X6) is also suitably used forbuilding materials and others.

7. Seventh Aspect

Hereinafter, the seventh aspect of the present invention is explained indetail. Foaming material (X7) related to the seventh aspect ischaracterized by containing propylene-based polymer (B7).

<Propylene-Based Polymer (A7)>

Propylene-based polymers (A7) optionally used in the seventh aspectinclude homopolypropylene and copolymers of propylene and at least oneC₂-C₂₀ α-olefin except propylene. The C₂-C₂₀ α-olefins except propyleneinclude α-olefins like those for isotactic polypropylene (A1) used inthe first aspect. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

Propylene-based polymer (A7) may contain structural units derived fromthese α-olefins in an amount of 35 mol % or less, and preferably 30 mol% or less. Here, the total of propylene-derived structural units andstructural units derived from α-olefins except propylene is 100 mol %.

The desirable melt flow rate (MFR) of propylene-based polymer (A7) is0.01 to 1,000 g/10 min, and preferably 0.05 to 100 g/10 min, asdetermined at 230° C. under a load of 2.16 kg in accordance with ASTMD1238.

The melting point of propylene-based polymer (A7) measured with adifferential scanning calorimeter is 100° C. or higher, preferably 100to 160° C., and more preferably 110 to 150° C.

Propylene-based polymer (A7) may be either isotactic or syndiotactic,but preferably isotactic, considering heat resistance and others.

There may be used, if necessary, two or more propylene-based polymers(A7) in combination, for example, two or more components different inmelting point or rigidity.

To attain desired properties, there may be used, as propylene-basedpolymer (A7), one or more polymers selected from homopolypropylene withexcellent heat resistance (publicly known, generally copolymerized with3 mol % or less of comonomers except propylene), block polypropylenewith excellent balance of heat resistance and flexibility (publiclyknown, generally containing 3 to 30 wt % of n-decane-soluble rubbercomponents), and random polypropylene with excellent balance offlexibility and transparency (publicly known, generally having a meltingpeak of 100° C. or higher and preferably 110° C. to 150° C. as measuredwith a differential scanning calorimeter DSC).

Such propylene-based polymer (A7) can be produced by methods similar tothose for producing isotactic polypropylene (A1) used in the firstaspect.

Foaming material (X7) of the seventh aspect containing component (A7)attains excellent scratch resistance and permanent compression set, inparticular.

<Propylene-Based Polymer (B7)>

Propylene-based polymers (B7) used in the seventh aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. The C₂-C₂₀ α-olefins except propylene includethe same α-olefins as those for propylene-based polymer (A7). Also, thepreferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

In propylene-based polymer (B7), the content of propylene-derivedstructural units is generally 40 to 100 mol %, preferably 40 to 99 mol%, more preferably 40 to 92 mol %, and still more preferably 50 to 90mol %; and the content of structural units derived from the C₂-C₂₀α-olefin (except propylene) used as a co-monomer is generally 0 to 60mol %, preferably 1 to 60 mol %, more preferably 8 to 60 mol %, andstill more preferably 10 to 50 mol %, wherein the total ofpropylene-units and C₂-C₂₀ α-olefin-units is 100 mol %).

The melting point of propylene-based polymer (B7) is lower than 120° C.or not observed, and preferably not higher than 100° C. or not observed,as measured with a a differential scanning calorimeter (DSC). Here,“melting point is not observed” means that any melting endothermic peakof crystal with a melting endothermic entalpy of crystal of 1 J/g ormore is not observed in the temperature range of −150 to 200° C. Themeasurement conditions are as described in Examples of the seventhaspect.

The intrinsic viscosity [η] of propylene-based polymer (B7) is generally0.01 to 10 dl/g, and preferably 0.05 to 10 dl/g as measured in decalinat 135° C.

Propylene-based polymer (B7) preferably has the same triad tacticity(mm-fraction) as propylene/ethylene/α-olefin copolymer (B1) used in thefirst aspect, whereby the same effect is obtained.

Namely, the triad tacticity (mm-fraction) of propylene-based polymer(B7) determined by ¹³C-NMR is preferably 85% or more, more preferably85% to 97.5%, still more preferably 87% to 97%, and particularlypreferably 90% to 97%. Polymer (B7) with the above range of triadtacticity (mm-fraction) is preferred for the seventh aspect, becauseexcellent balance of flexibility and mechanical strength is attained, inparticular. The mm-fraction can be determined by the method described inWO 04/087775 from Page 21 line 7 to Page 26 line 6.

The methods for producing propylene-based polymer (B7) are notparticularly limited to, but include methods similar to those forproducing propylene-based polymer (B5) used in the fifth aspect.

It is desirable that propylene-based polymer (B7) has additionallyindependently the following properties.

The Shore A hardness of propylene-based polymer (B7) is preferably 30 to80, and more preferably 35 to 70.

The stress at 100% elongation (M100) of propylene-based polymer (B7) isgenerally 4 MPa or less, preferably 3 MPa or less, and more preferably 2MPa or less, as measured in accordance with JIS K6301 at a span distanceof 30 mm and a tensile speed of 30 mm/min with a JIS #3 dumbbell at 23°C. With the above range of M100, propylene polymer (B7) providesexcellent flexibility and rubber elasticity.

Propylene-based polymer (B7) preferably has the same properties aspropylene/ethylene/α-olefin copolymer (B1) used in the first aspectconcerning crystallinity, glass transition temperature Tg, and molecularweight distribution (Mw/Mn). These properties provide the same effects.

For example, the molecular weight distribution (Mw/Mn, relative topolystyrene standards, Mw: weight-average molecular weight, Mn:number-average molecular weight) of propylene-based polymer (B7)measured by GPC is preferably 4.0 or less, more preferably 3.0 or less,and still more preferably 2.5 or less.

When propylene-based polymer (B7) shows a melting point (Tm in ° C.) inthe endothermic curve recorded with a differential scanning calorimeter(DSC), the melting endothermic entalpy, ΔH, is generally 30 J/g or less,and also satisfies the same relation between C₃ content (mol %) andmelting endothermic entalpy ΔH (J/g) as that ofpropylene/ethylene/α-olefin copolymer (B1) used in the first aspect.

Preferred examples of propylene-based polymer (B7) include,specifically, propylene/ethylene/C₄-C₂₀ α-olefin copolymer (B7-1) below.Crosslinked foams obtained using propylene/ethylene/C₄-C₂₀ α-olefincopolymer (B7-1) are excellent in flexibility and properties ofpermanent compression set and mechanical strength.

In propylene/ethylene/C₄-C₂₀ α-olefin copolymer (B7-1), the content ofpropylene-derived structural units is 45 to 92 mol %, preferably 56 to90 mol %, and more preferably 61 to 86 mol %; the content ofethylene-derived structural units is 5 to 25 mol %, preferably 5 to 14mol %, and more preferably 8 to 14 mol %; and the content of C₄-C₂₀α-olefin-derived structural units is 3 to 30 mol %, preferably 5 to 30mol %, and more preferably 6 to 25 mol %, wherein the total ofpropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀ α-olefin-derived structural units is 100 mol %. As the C₄-C₂₀α-olefin, 1-butene is particularly preferred.

When the composition contains propylene-based polymer (A7),propylene/ethylene/C₄-C₂₀ α-olefin copolymer (B7-1) containingpropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀α-olefin-derived structural units in the above contents hasgood compatibility with (A7), providing crosslinked foams excellent inpermanent compression set and scratch resistance.

With the contents of structural units derived from propylene, ethylene,and C₄-C₂₀ α-olefins in the above preferred ranges, resultant formingmaterials can provide foams with more excellent balance of flexibility,permanent compression set, and scratch resistance. Further,incorporating component (B7) in foaming material (X7) imparts foams tolow resilience.

<Ethylene/α-Olefin Copolymer (C7)>

Ethylene/α-olefin copolymer (C7) optionally used in the seventh aspectis a non-crystalline or low-crystalline random or block copolymercomposed of ethylene and a C₃-C₂₀ α-olefin. Its density (evaluated inaccordance with ASTM D1505) is generally 0.857 g/cm³ or more and 0.910g/cm³ or less, preferably 0.860 to 0.905 g/cm³, and more preferably0.880 to 0.905 g/cm³; and its melt flow rate (MFR measured in accordancewith ASTM D1238 at 190° C. under a load of 2.16 kg) is generally 0.1 to40 g/10 min, and preferably 0.5 to 20 g/10 min.

The C₃-C₂₀ α-olefins include, specifically, propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene,1-eicosene, 4-methyl-1-pentene, and others. Among them, preferred areC₃-C₁₀ α-olefins, and particularly preferred are propylene, 1-butene,1-hexene, and 1-octene. These α-olefins may be used alone or incombination of two or more.

Desirably, ethylene/α-olefin copolymer (C7) contains 75 to 95 mol % ofethylene-derived structural units and 5 to 25 mol % of C₃-C₂₀α-olefin-derived structural units, wherein the total of ethylene-unitsand α-olefin-units is 100 mol %.

Ethylene/α-olefin copolymer (C7) may further contain, besides theseunits, units derived from other polymerizable monomers, as long as theobjectives of the seventh aspect are not impaired.

Ethylene/α-olefin copolymers (C7) include, specifically,ethylene/propylene copolymer, ethylene/1-butene copolymer,ethylene/propylene/1-butene copolymer,ethylene/propylene/ethylidenenorbornene copolymer, ethylene/1-hexenecopolymer, and ethylene/1-octene copolymer. Among them, preferably usedare ethylene/propylene copolymer, ethylene/1-butene copolymer,ethylene/1-hexene copolymer, ethylene/1-octene copolymer, and others.Ethylene/1-butene copolymer is particularly preferably used. Thesecopolymers may be random or block copolymers, but random copolymers arepreferable in particular.

The crystallinity of ethylene/α-olefin copolymer (C7) is generally 40%or less, and preferably 10 to 30% as measured by X-ray diffractometry.

In ethylene/α-olefin copolymer (C7), the desired molecular weightdistribution (Mw/Mn) determined by gel permeation chromatography (GPC)is 1.5 to 3.0, and preferably 1.7 to 2.5. When ethylene/α-olefincopolymer (C7) with this range of molecular weight distribution (Mw/Mn)is used, foaming material (X7) obtained provides foams excellent inpermanent compression set and filling property. Ethylene/α-olefincopolymer (C7) described above exhibits generally properties aselastomers.

With ethylene/α-olefin copolymer (C7), it is desirable that the ratioMFR₁₀/MFR₂, wherein MFR₁₀ and MFR₂ are melt flow rates under a load of10 kg and a load of 2.16 kg, respectively, measured at 190° C. inaccordance with ASTM D1238, satisfies following relations:

MFR₁₀/MFR₂≧6.0,

preferably

7≦MRT₁₀/MFR₂≦15, and at the same time,

the molecular weight distribution (Mw/Mn) and MRT₁₀/MFR₂ satisfy thefollowing relation:

Mw/Mn+5.0<MFR ₁₀ /MFR ₂

These relations ensure availability of foaming material (X7) capable ofpreparing foams (uncrosslinked or crosslinked) that is foamed at highfoaming ratio, i.e. having low specific gravity, highly elastic, andexcellent in permanent compression set and filling property.

Desirably, in the ¹³C-NMR spectrum of ethylene/α-olefin copolymer (C7),the intensity ratio of Tαβ to Tαα (Tαβ/Tαα) is 0.5 or less, andpreferably 0.4 or less.

Here, Tαα and Tαβ are the peak intensities of CH₂ in the structuralunits derived from an α-olefin having 3 or more carbon atoms, and thesetwo kinds of CH₂ groups are different in the position relative to thetertiary carbon atom as shown below.

Tαβ/Tαα is determined as follows. For example, the ¹³C-NMR spectrum ofethylene/α-olefin copolymer (C7) is recorded on an NMR spectrometer(JEOL-GX270, manufactured by JEOL Ltd.) with a solution containing 5 wt% of the sample in hexachlorobutadiene/benzene-d₆ (2/1 by volume) mixedsolvent, at 67.8 MHz at 25° C. using benzene-d₆ (128 ppm) as reference.The obtained ¹³C-NMR spectrum is analyzed in accordance with proposalsby Lindeman & Adams (Analysis Chemistry 43, 1245 (1971)) and J. C.Randall (Reviews in Macromolecular Chemistry and Physics, C29, 201(1989)) to obtain Tαβ/Tαα.

It is desirable that the B-value of ethylene/α-olefin copolymer (C7) is0.9 to 1.5 and preferably 0.95 to 1.2, which is obtained from the¹³C-NMR spectrum using equation (7-1) below:

B-value=[P _(OE)]/(2·[P _(E) ][P _(O)])  (7-1),

(in the formula, [P_(E)] is the mole fraction of ethylene-derivedstructural units in the copolymer; [P_(O)] is the mole fraction ofα-olefin-derived structural units in the copolymer; and [P_(OE)] is theratio of number of ethylene-α-olefin dyad to the total number of dyadsin the copolymer).

This B-value is an index representing the distribution of ethylene unitsand the C₃-C₂₀ α-olefin units in the ethylene/α-olefin copolymer, and isobtained according to papers by J. C. Randall (Macromolecules, 15, 353(1982)) and J. Ray et al. (Macromolecules, 10, 773(1977)).

The B-value of ethylene/α-olefin copolymer (C7) is typically determinedby acquiring the ¹³C-NMR spectrum of a sample solution, in which about200 mg of the ethylene/α-olefin copolymer is homogeneously dissolved in1 mL of hexachlorobutadiene, in a 10-mmΦ sample tube at measurementtemperature of 120° C. with measurement frequency of 25.05 MHz, spectrumwidth of 1500 Hz, pulse repetition interval of 4.2 sec, and pulse widthof 6 μsec.

A larger B-value means that each blocked chain of ethylene or α-olefincopolymer is shorter, that is, the distribution of ethylene and α-olefinis more uniform, or the composition distribution in copolymer rubber isnarrower. As the B-value is more lowered from 1.0, the ethylene/α-olefincopolymer has a wider composition distribution and hence disadvantagessuch as difficulties in handling.

Ethylene/α-olefin copolymer (C7) can be produced by conventional methodsusing a vanadium catalyst, a titanium catalyst, or a metallocenecatalyst. In particular, solution polymerization described in JapanesePatent Laid-Open Publication No. S62-121709 and others are preferable.

Ethylene/α-olefin copolymer (C7) is used, if any, in an amount of 1 to1900 parts by weight, preferably 5 to 1000 parts by weight, and morepreferably 5 to 500 parts by weight, relative to 100 parts by weight ofthe total of propylene-based polymer (B7) and propylene-based polymer(A7), which is optionally used. The composition containing such amountof component (C7) provides foams having low specific gravity and lowpermanent compression set in particular. This effect is particularlyremarkable in use for crosslinked foams.

<Ethylene/Polar Monomer Copolymer (D7)>

As the polar monomer used for ethylene/polar monomer copolymer (D7)optionally used in the seventh aspect, there may be mentioned,unsaturated carboxylic acids, their salts, their esters, their amides,vinyl esters, carbon monoxide, and others. Specifically, the polarmonomer may be one compound or two or more compounds selected fromunsaturated carboxylic acids such as acrylic acid, methacrylic acid,fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate,maleic anhydride, and itanonic anhydride; salts of such unsaturatedcarboxylic acid with a mono-valent metal such as lithium, sodium, andpotassium; salts of such unsaturated carboxylic acid with a poly-valentmetal such as magnesium, calcium, and zinc; unsaturated carboxylicesters such as methyl acrylate, ethyl acrylate, isopropyl acrylate,isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methylmethacrylate, ethyl methacrylate, isobutyl methacrylate, and dimethylmaleate; vinyl esters such as vinyl acetate and vinyl propionate; carbonmonoxide; sulfur dioxide; and others.

Ethylene/polar monomer copolymers (D7) include, more specifically,ethylene/unsaturated acid copolymers such as ethylene/acrylic acidcopolymer and ethylene/methacrylic acid copolymer; ionomers wherein partor all of carboxyl protons in said ethylene/unsaturated carboxylic acidcopolymer are replaced by the metals described above;ethylene/unsaturated carboxylate copolymers such as ethylene/methylacrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methylmethacrylate copolymer, ethylene/isobutyl acrylate copolymer, andethylene/n-butyl acrylate copolymer; ethylene/unsaturatedcarboxylate/unsaturated carboxylic acid copolymers such asethylene/isobutyl acrylate/methacrylic acid copolymer andethylene/n-butyl acrylate/methacrylic acid copolymer; ionomers whereinpart or all of carboxyl protons in said ethylene/unsaturatedcarboxylate/unsaturated carboxylic acid copolymer are replaced by themetals described above; ethylene/vinyl ester copolymers such asethylene/vinyl acetate copolymer; and others.

In particular, (D7) of these, copolymers of ethylene and a polar monomerselected from unsaturated carboxylic acids, their salts, their esters,and vinyl acetate are preferable; ionomers derived fromethylene/(meth)acrylic acid copolymer, ionomers derived fromethylene/(meth)acrylic acid/(meth)acrylate copolymer, or ethylene/vinylacetate copolymer are more preferable; and ethylene/vinyl acetatecopolymers are still more preferable.

In ethylene/polar monomer copolymer (D7), the polar monomer content is 1to 50 wt %, and preferably 5 to 45 wt %, although varied with the polarmonomer. It is desirable that such ethylene/polar monomer copolymer (D7)has a melt flow rate (MFR) at 190° C. under a load of 2160 g of 0.05 to500 g/10 min, and preferably 0.5 to 20 g/10 min, consideringmoldability, mechanical strength, and others.

The copolymers of ethylene with unsaturated carboxylic acids,unsaturated carboxylates, vinyl ester, or the like can be obtained byradical copolymerization at high temperature under high pressure. Thecopolymers of ethylene and metal salts of unsaturated carboxylic acids(ionomers) can be obtained by reacting the ethylene/unsaturatedcarboxylic acid copolymers with the corresponding metal compounds.

When ethylene/vinyl acetate copolymer is used as ethylene/polar monomercopolymer (D7), the vinyl acetate content is 10 to 30 wt %, preferably15 to 30 wt %, and more preferably 15 to 25 wt % in the ethylene/vinylacetate copolymer.

The melt flow rate (MFR, measured in accordance with ASTM D1238, at 190°C. under a load of 2.16 kg) of ethylene/vinyl acetate copolymer (D7) is0.1 to 50 g/10 min, preferably 0.5 to 20 g/10 min, and more preferably0.5 to 5 g/10 min.

When ethylene/α-olefin copolymer (C7) is used, ethylene/polar monomercopolymer (D7) is used in an amount of 1 to 1900 parts by weight,preferably 5 to 1000 parts by weight, and more preferably 5 to 500 partsby weight, relative to 100 parts by weight of the total ofpropylene-based polymer (B7) and propylene-based polymer (A7) optionallyused.

When ethylene/polar monomer copolymer (D7) is an ethylene/unsaturatedcarboxylic acid copolymer, blending of the copolymer in the above ratioprovides elastomer compositions capable of forming crosslinked foamswith excellent adhesion to other layers made of polyurethane, rubber,leather, or the like. In addition, when ethylene/polar monomer copolymer(D7) is blended in the above ratio, the resulting foam layer isexcellent in adhesion to other layers made of polyurethane, rubber,leather, or the like, and suitable for lamination.

<Material for Foam (X7)>

Foaming material (X7) of the seventh aspect contains at leastpropylene-based polymer (B7) and may further contain propylene-basedpolymer (A7), if necessary. Foaming material (X7) is preferably acomposition containing 30 to 100 parts by weight of propylene-basedpolymer (B7) and 0 to 70 parts by weight of propylene-based polymer(A7), the melting point of (A7) being 100° C. or higher as measured witha differential scanning calorimeter (here, the total of (A7) and (B7) is100 parts by weight). More preferably, the foaming material contains 30to 99 parts by weight of propylene-based polymer (B7) and 1 to 70 partsby weight of propylene-based polymer (A7); still more preferably, 50 to95 parts by weight of propylene-based polymer (B7) and 5 to 50 parts byweight of propylene-based polymer (A7); and particularly preferably, 70to 90 parts by weight of propylene-based polymer (B7) and 10 to 30 partsby weight of propylene based-polymer (A7).

Foaming material (X7) of the seventh aspect is preferably a compositioncontaining 1 to 1900 parts by weight of ethylene/α-olefin copolymer (C7)and/or 1 to 1900 parts by weight of ethylene/polar monomer copolymer(D7) relative to 100 parts by weight of the total of propylene-basedpolymer (B7) and if any, propylene-based polymer (A7). Such compositionsinclude, for example,

(i) composition containing 1 to 1900 parts by weight ofethylene/α-olefin copolymer (C7) relative to 100 parts by weight of thetotal of propylene-based polymer (B7) and if any, propylene-basedpolymer (A7);

(ii) composition containing 1 to 1900 parts by weight of ethylene/polarmonomer copolymer (D7) relative to 100 parts by weight of the total ofpropylene-based polymer (B7) and if any, propylene-based polymer (A7);and

(iii) composition containing 1 to 1900 parts by weight ofethylene/α-olefin copolymer (C7) and 1 to 1900 parts by weight ofethylene/polar monomer copolymer (D7) relative to 100 parts by weight ofthe total of propylene-based polymer (B7) and if any, propylene-basedpolymer (A7).

More preferred embodiments include a composition containing 5 to 1000parts by weight of ethylene/α-olefin copolymer (C7) among composition(i), a composition containing 5 to 1000 parts by weight ofethylene/α-olefin copolymer (C7) among composition (iii), a compositioncontaining 5 to 1000 parts by weight of ethylene/α-olefin copolymer (C7)and 5 to 1000 parts by weight of ethylene/polar monomer copolymer (D7)among composition (iii), and others.

<Foaming Agent (E7)>

Foaming agents (E7) optionally used in the seventh aspect includechemical foaming agents, specifically, organic thermally decomposablefoaming agents including azo compounds such as azodicarbonamide (ADCA),1,1′-azobis(1-acetoxy-1-phenylethane), dimethyl 2,2′-azobisbutyrate,dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis(2,4,4-trimethylpentane),1,1′-azobis(cyclohexane-1-carbonitrile), and2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]; nitrosocompounds such as N,N′-dinitrosopentamethylenetetramine (DPT); hydrazinederivatives such as 4,4′-oxybis(benzenesulfonylhydrazide) anddiphenylsulfone-3,3′-disulfonylhydrazide; semicarbazides such asp-toluenesulfonylsemicarbazide; and trihydrazinotriazine, and alsoinorganic thermally decomposable foaming agents includinghydrogencarbonates such as sodium hydrogencarbonate and ammoniumhydrogencarbonate; carbonates such as sodium carbonate and ammoniumcarbonate; nitrites such as ammonium nitrite, and hydrogen compounds.Among these, azodicarbonamide (ADCA) and sodium hydrogencarbonate areparticularly preferable.

As foaming agent (E7) in the seventh aspect, there may also be usedphysical foaming agents (foaming agents do not necessarily generatebubbles with chemical reaction), for example, organic physical formingagents including aliphatic hydrocarbons such as methanol, ethanol,propane, butane, pentane, and hexane; chlorohydrocarbons such asdichloroethane, dichloromethane, and carbon tetrachloride; andchlorofluorohydrocarbons such as CFCs, and also inorganic physicalfoaming agents including air, carbon dioxide, nitrogen, argon, andwater. Among these, carbon dioxide, nitrogen, and argon are excellent,because they can dispense with vaporization process, are not expensive,and quite hardly cause environmental pollution or ignition.

Since the physical foaming agent generates no decomposition residue,mold staining can be prevented when the composition is crosslinkedfoamed. In addition, the physical foaming agent is not powdery and hencereadily mixed in kneading. Further, with the physical foaming agent,resultant crosslinked foams will not generate offensive odors (forexample, ammonia odor generated on decomposition of ADCA).

In the seventh aspect, the chemical foaming agent described above may beused together, as long as no adverse effect such as offensive odor ormold staining comes about.

For using a physical foaming agent in small scale production, the agent,such as carbon dioxide and nitrogen, stored in a cylinder may besupplied to an injection molding machine, an extrusion molding machine,or the like either through a pressure regulator or while beingpressurized with a pump or the like.

In facilities for large-scale production of foamed articles, a tank forstoring liquid carbon dioxide, liquid nitrogen, or the like isinstalled, the liquid is vaporized through a heat exchanger, and the gasis supplied to an injection molding machine, an extrusion moldingmachine, or the like through tubing and a pressure regulator.

In the case of a liquid physical foaming agent, the pressure of agent instorage is preferably 0.13 to 100 MPa. If the pressure is too low, theagent would sometimes fail to be supplied into an injection moldingmachine, an extrusion molding machine, or the like after reducingpressure. If the pressure is too high, the storage tank is required tohave high pressure resistance, whereby the tank sometimes becomes largein size and complex in structure. The “pressure of agent in storage”defined here is the pressure at which the agent is supplied to thepressure regulator after vaporized.

When the chemical foaming agent is used as foaming agent (E7), thechemical foaming agent is used in a ratio of generally 1 to 40 parts byweight and preferably 2 to 20 parts by weight relative to 100 parts byweight of the total of propylene-based polymer (A7), propylene-basedpolymer (B7), ethylene/α-olefin copolymer (C7), and ethylene/polarmonomer copolymer (D7). Note that, the components other than (B7) areoptional, so that the amount of one or more of components (A7), (C7),and (D7) may be 0 parts by weight. The amount of chemical foaming agentis adjusted as appropriate according to a desired foaming ratio, becausethe volume of gas generated from the foaming agent varies with speciesand/or grade of the foaming agent to be used.

When the physical foaming agent is used as foaming agent (E7), theamount of physical foaming agent is adjusted as appropriate according toa desired foaming ratio.

In the seventh aspect, a foaming auxiliary may be optionally usedtogether with foaming agent (E7). The foaming auxiliary has functionssuch as lowering the decomposition temperature of foaming agent (E7),promoting the decomposition, and homogenizing bubble generation. Suchfoaming auxiliaries include zinc oxide (ZnO), zinc stearate, organicacids such as salicylic acid, phthalic acid, stearic acid, and oxalicacid, urea or its derivatives, and others.

<Organic Peroxide (F7)>

Organic peroxides (F7) optionally used as the crosslinker in the seventhaspect include, specifically, dicumyl peroxide, di-t-butyl peroxide,2,5-dimethyl-2,5-di-(t-butylperoxy)hexane,2,5-dimethyl-2,5-(t-butylperoxy)-3-hexyne,1,3-bis(t-butylperoxyisopropyl)benzene,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoylperoxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxy benzoate, t-butylperbenzoate, t-butylperoxy isopropyl carbonate, diacetyl peroxide,lauloyl peroxide, t-butyl cumyl peroxide, and others.

The amount of organic peroxide (F7) used in the seventh aspect isgenerally 0.1 to 1.5 parts by weight, and preferably 0.2 to 1.0 part byweight, relative to 100 parts by weight of the total of propylene-basedpolymer (A7), propylene-based polymer (B7), ethylene/α-olefin copolymer(C7), and ethylene/polar monomer copolymer (D7). Note that, thecomponents other than (B7) are optional, so that the amount of one ormore of components (A7), (C7), and (D7) may be 0 parts by weight. Use oforganic peroxide (F7) in the above ratio gives crosslinked foams havingappropriate structure of crosslinking. When organic peroxide (F7) isused in the above ratio together with crosslinking auxiliary (G7),crosslinked foams obtained have more appropriate structure ofcrosslinking.

<Crosslinking Auxiliary (G7)>

Crosslinking auxiliaries (G7) optionally used in the seventh aspectinclude, specifically, auxiliaries for peroxy-crosslinking such assulfur, p-quinonedioxime, p,p′-dibenzoylquinonedioxime,N-methyl-N,4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, andtrimethylolpropane-N,N′-m-phenylene dimaleimide; divinylbenzene,triallyl cyanurate (TAC), and triallyl isocyanurate (TRIC). Crosslinkingauxiliaries (G7) also include multifunctional methacrylate monomers suchas ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,and allyl methacrylate; multifunctional vinyl monomers such as vinylbutyrate and vinyl stearate; and others. Among them, triallyl cyanurate(TAC) and triallyl isocyanurate (TRIC) are preferred.

In the seventh aspect, the desirable weight ratio of organic peroxide(F7) to crosslinking auxiliary (G7) ((F7)/(G7)) is 1/30 to 20/1, andpreferably 1/20 to 10/1.

<Preparation of Material for Foam (X7)>

Foaming material (X7) related to the seventh aspect of is anuncrosslinked and unfoamed material and may be in a molten state orsolidified by cooling into pellets or sheets.

Pellets of foaming material (X7) described above are prepared, forexample, as follows: at first, there are mixed required componentsselected from propylene-based polymer (B7), which is the copolymer ofpropylene and at least one C₂-C₂₀ α-olefin except propylene and whosemelting point is lower than 100° C. or not observed with a differentialscanning calorimeter, propylene-based polymer (A7) having the meltingpoint of 100° C. or higher as measured with a differential scanningcalorimeter, ethylene/α-olefin copolymer (C7), ethylene/polar monomercopolymer (D7), foaming agent (E7), organic peroxide (F7), andoptionally crosslinking auxiliary (G7) and the foaming auxiliary, in theabove ratios, with a Henschel mixer or the like; the resulting mixtureis melted and plasticized with a kneader, such as Banbury mixer, roll,and extruder, at a temperature at which foaming agent (E7) and/ororganic peroxide (F7) are not decomposed, so that the components areuniformly mixed and dispersed; and then, the mixture is processed with apelletizer to obtain pellets.

Foaming material (X7) may optionally contain, besides the abovecomponents, various additives such as filler, heat stabilizers,weathering stabilizers, flame retardants, hydrochloric acid absorbers,and pigments as long as the objectives of the seventh aspect are notimpaired.

The sheet (uncrosslinked and unfoamed foaming sheet) of foaming material(X7) is prepared, for example, by molding the pelletized compositionprepared above using an extruder or a calendar molding machine.Alternative methods for preparing the sheet include a method of kneadingcomponents of the above composition with a Brabender mill or the like,followed by forming the kneaded material into a sheet with a calendarroll or a press molding machine; a method of kneading the componentsusing an extruder, followed by molding of the kneaded material through aT-die or circular die into a sheet; and others.

<Foam>

The foam related to the seventh aspect is obtained by foaming orcrosslinking foaming of foaming material (X7) described above, generallyunder conditions of 130 to 200° C., 30 to 300 kgf/cm², and 10 to 90 min.However, the forming or crosslink forming time may be adjusted out ofthe above range as appropriate, because it depends on the thickness ofmold.

The foam or crosslinked foam of the seventh aspect may be a foam orcrosslinked foam obtained by compression molding of a molded article,which has been foamed or crosslinked foamed under the above conditions,at 130 to 200° C., under 30 to 300 kgf/cm², for 5 to 60 min, at acompression ratio of 1.1 to 3, and preferably 1.3 to 2.

With the foam or crosslinked foam, the specific gravity (JIS K7222) isgenerally 0.6 or less, preferably 0.03 to 0.4, more preferably 0.03 to0.25, and still more preferably 0.05 to 0.25; while the surface hardness(Asker C hardness) is generally 20 to 80, and preferably 30 to 65. Thegel fraction of crosslinked foam is desirably 70% or more, and generally70% to 95%.

The crosslinked foam of the seventh aspect with such properties hassmall permanent compression set, high tear strength, excellent vibrationdamping property, and excellent scratch resistance.

Here, the gel fraction (gel content, xylene-insoluble fraction) ismeasured as follows.

A weighed sample of crosslinked foam is cut finely into chips, theresulting chips are put in a sealed vessel with p-xylene, and p-xyleneis refluxed under normal pressure for 3 hours. Specifically, 1.5 g ofthe sample is put in 100 cc of p-xylene at 140° C., which is refluxedfor 3 hours. Then, insoluble part is collected with a 325-mesh screen.

After that, the resulting sample (insoluble part) is completely dried.The “corrected final weight (Y)” is calculated by subtracting the weightof xylene-insoluble part other than polymers (for example, filler,fillings, pigments, etc.) from the weight of dried residue.

On the other hand, the “corrected initial weight (X)” is calculated bysubtracting the weight of xylene-soluble part other than polymers (forexample, stabilizers, etc.) and the weight of xylene-insoluble partother than polymers (for example, filler, fillings, pigments, etc.) fromthe sample weight.

Now, the gel fraction (xylene-insoluble content) is determined by thefollowing equation:

Gel fraction (wt %)=([corrected final weight (Y)]÷[corrected initialweight (X)])×100

<Preparation of Foam>

The foam (uncrosslinked or crosslinked foam) related to the seventhaspect is prepared, for example, by the following method.

The sheet of foaming material (X7) related to the seventh aspect can beobtained, for example, from a mixture described in the section ofpreparation of foaming material (X7), using a calendar molding machine,press molding machine, or T-die extruder. The sheet is required to bemolded at a temperature below the decomposition temperatures of foamingagent (E7) and organic peroxide (F7). Specifically, the sheet ispreferably molded under such conditions that the temperature of meltedfoaming material (X7) is 100 to 130° C.

The sheet formed from foaming material (X7) by the above method is cutto reduce its volume to 1.0 to 1.2 times of the volume of mold and thecut material is inserted into the mold kept at 130 to 200° C. A primaryfoam (uncrosslinked or crosslinked foam) is prepared under suchconditions that the clamping pressure of mold is 30 to 300 kgf/cm² andthe hold time is 10 to 90 min, although the hold time may be adjustedbeyond the above range as appropriate, because it depends on thethickness of mold.

The mold for producing the above foam is not particularly limited on itsshape, but a mold with a shape capable of forming sheets is generallyused. This mold is required to have a totally closed structure toprevent leakage of the resin melt and gas generated by decomposition ofthe foaming agent. The mold frame preferably has tapered inside face foreasy release of resins.

The primary foam obtained by the above method is compression-molded intoa predetermined shape (prepare a secondary foam). The compressionmolding is conducted at a mold temperature of 130 to 200° C., under aclamping pressure of 30 to 300 kgf/cm², for a compressing time of 5 to60 min, at a compression ratio of 1.1 to 3.0.

The method for obtain the crosslinked foam through crosslinking usingionizing irradiation is as follows. Firstly, the necessary componentsselected from propylene-based polymer (B7), which is the copolymer ofpropylene and at least one C₂-C₂₀ α-olefin except propylene and whosemelting point is lower than 100° C. or not observed with a differentialscanning calorimeter, propylene-based polymer (A7) having a meltingpoint of 100° C. or higher as measured with a differential scanningcalorimeter, ethylene/α-olefin copolymer (C7), and ethylene/polarmonomer copolymer (D7) are melt-kneaded together with the organicthermally decomposable foaming agent as foaming agent (E7) and otheradditives at a temperature below the decomposition temperature of theorganic thermally decomposable foaming agent; then the resulting mixtureis molded, for example, in a sheet form to obtain a foaming sheet.

After the resulting sheet is exposed to ionizing radiation in apredetermined exposure dose for crosslinking, the crosslinked foamingsheet thus obtained is foamed by heating above the decompositiontemperature of the organic thermally decomposable foaming agent, wherebya crosslinked foamed sheet is obtained.

The ionizing radiations include α-rays, β-rays, γ-rays, electron beam,neutron beam, and X-rays. Among these, γ-rays from cobalt-60 andelectron beam are preferably used.

The product shapes of the foam include, for example, sheet, heavy board,net, and mold.

From the crosslinked foam (primary foam) thus obtained, a secondarycrosslinked foam with the above properties can be prepared, in a similarmanner to that in producing the above secondary foam.

<Laminate>

The laminate related to the seventh aspect of invention contains a layerof the above foam (uncrosslinked or crosslinked foam) and a layer madeof at least one material selected from the group consisting ofpolyolefin, polyurethane, rubber, leather, and artificial leather.

The above polyolefin, polyurethane, rubber, leather, and artificialleather are not particularly limited; there may be used conventionalpublicly known polyolefin, polyurethane, rubber, leather, and artificialleather. The laminate is suitably used especially for footwear andfootwear components.

<Footwear and Footwear Components>

The footwear and footwear components of the seventh aspect are composedof the above foam (uncrosslinked or crosslinked) or laminate. Thefootwear components include, for example, shoe soles, shoe mid soles,inner soles, soles, and sandals.

8. Eighth Aspect

Hereinafter, the eighth aspect of invention is explained in detail.

<Propylene-Based Polymer (A8)>

Propylene-based polymers (A8) used in the eighth aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. The C₂-C₂₀ α-olefins except propylene includethe same as those for isotactic polypropylene (A1) used in the firstaspect. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

The structural units derived from these α-olefins may be contained in aratio of 35 mol % or less and preferably 30 mol % or less inpropylene-based polymer (A8).

It is desirable that the melt flow rate (MFR) of propylene-based polymer(A8), as measured at 230° C. under a load of 2.16 kg in accordance withASTM D1238, is 0.01 to 1000 g/10 min, and preferably 0.05 to 100 g/10min.

The melting point of propylene-based polymer (A8) measured with adifferential scanning calorimeter is 100° C. or higher, preferably 100to 160° C., and more preferably 110 to 150° C.

Propylene-based polymer (A8) may be either isotactic or syndiotactic,but the isotactic structure is preferred considering heat resistance andothers.

There may be used, if necessary, a plurality of propylene-based polymers(A8), for example, two or more components different in melting point orrigidity.

To obtain desired properties, there may be used, as propylene-basedpolymer (A8), one polymer or a combination of polymers selected fromhomopolypropylene excellent in heat resistance (publicly known,generally containing 3 mol % or less of copolymerized components exceptpropylene), block polypropylene excellent in balance of heat resistanceand flexibility (publicly known, generally containing 3 to 30 wt % ofn-decane-soluble rubber components), and random polypropylene excellentin balance of flexibility and transparency (publicly known, generallyhaving a melting peak of 100° C. or higher and preferably 110° C. to150° C. as measured with a differential scanning calorimeter DSC).

Such propylene-based polymer (A8) can be produced in a similar manner tothat for producing isotactic polypropylene (A1) used in the firstaspect.

<Soft Propylene-Based Copolymer (B8)>

Soft propylene-based copolymer (B8) used in the eighth aspect is acopolymer of propylene and at least one C₂-C₂₀ α-olefin exceptpropylene. Shore A hardness thereof is 30 to 80 and preferably 35 to 70,and melting point thereof is lower than 100° C. or not observed whenmeasured with a differential scanning calorimeter (DSC). Here, “meltingpoint is not observed” means that any melting endothermic peak ofcrystal having a melting endothermic enthalpy of crystal of 1 J/g ormore is not observed in the temperature range of −150 to 200° C. Themeasurement conditions are as described in Examples.

In soft propylene-based copolymer (B8), the α-olefin used as aco-monomer is preferably ethylene and/or a C₄-C₂₀ α-olefin.

In soft propylene-based copolymer (B8), preferably, the content ofpropylene-derived units is 45 to 92 mol % and preferably 56 to 90 mol %,and the content of units derived from the α-olefin used as a co-monomeris 8 to 55 mol % and preferably 10 to 44 mol %.

It is desirable that the melt flow rate (MFR) of soft propylene-basedcopolymer (B8), as measured at 230° C. under a load of 2.16 kg inaccordance with ASTM D1238, is 0.01 to 100 g/10 min and preferably 0.05to 50 g/10 min.

The method for producing soft propylene-based copolymer (B8) is notparticularly limited; it may be produced by polymerizing propylene orcopolymerizing propylene and another α-olefin in the presence of apublicly known catalyst used for stereospecific olefin polymerizationcapable of yielding an isotactic or syndiotactic polymer, for example, acatalyst mainly composed of a solid titanium component and anorganometallic compound, or a metallocene catalyst containing ametallocene compound as one of catalyst components. Preferably, asdescribed later, the copolymer is produced by copolymerizing propylene,ethylene, and a C₄-C₂₀ α-olefin in the presence of the metallocenecatalyst.

It is desirable that soft propylene-based polymer (B8) has additionallyindependently the following properties.

Soft propylene-based copolymer (B8) preferably has the same propertiesas propylene/ethylene/α-olefin copolymer (B1) used in the first aspectconcerning triad tacticity (mm-fraction), stress at 100% elongation,crystallinity, glass transition temperature Tg, and molecular weightdistribution (Mw/Mn). These properties provide the same effects.

For instance, the triad tacticity (mm-fraction) of soft propylene-basedcopolymer (B8) determined by ¹³C-NMR is preferably 85% or more, morepreferably 85% to 97.5%, still more preferably 87% to 97%, andparticularly preferably 90 to 97%. With the above range of triadtacticity (mm-fraction), the composition is excellent particularly inbalance of flexibility and mechanical strength, which is preferable inthe present invention. The mm-fraction can be determined by the methoddescribed in WO 2004/087775 pamphlet from Page 21 line 7 to Page 26 line6.

The molecular weight distribution (Mw/Mn, relative to polystyrenestandards, Mw: weight average molecular weight, Mn: number averagemolecular weight) of soft propylene-based copolymer (B8), as measured byGPC, is preferably 4.0 or less, more preferably 3.0 or less, and stillmore preferably 2.5 or less.

When soft propylene-based copolymer (B8) has a melting point (Tm in °C.) in the endothermic curve recorded with a differential scanningcalorimeter (DSC), its melting endothermic entalpy, ΔH, is generally 30J/g or less and the same relation is satisfied between C₃ content (mol%) and melting endothermic entalpy ΔH (J/g) as that inpropylene/ethylene/α-olefin copolymer (B1) used in the first aspect.

Preferred examples of soft propylene-based copolymer (B8) include,specifically, propylene/ethylene/α-olefin copolymer (B8-1) below.Propylene/ethylene/α-olefin copolymer (B8-1) imparts flexibility, heatresistance, mechanical strength, and transparency, and is suitably used.

In propylene/ethylene/α-olefin copolymer (B8-1), the content ofpropylene-derived structural units is 45 to 92 mol %, preferably 56 to90 mol %, and more preferably 61 to 86 mol %; that of ethylene-derivedstructural units is 5 to 25 mol %, preferably 5 to 14 mol %, and morepreferably 8 to 14 mol %; and that of C₄-C₂₀ α-olefin-derived structuralunits is 3 to 30 mol %, preferably 5 to 30 mol %, and more preferably 6to 25 mol %. Of the α-olefins 1-butene is particularly preferable.

Propylene/ethylene/α-olefin copolymer (B8-1) containingpropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀ α-olefin-derived structural units in the above ratiosexhibits excellent compatibility with propylene-based polymer (A8),providing sufficient transparency, flexibility, heat resistance, andscratch resistance.

Further, with the above range of ratios of the structural units derivedfrom propylene, ethylene, and a C₄ to C₂₀ α-olefin, materials withexcellent balance of flexibility, heat resistance, and scratchresistance can be obtained.

<Coupling Agent (Y8)>

As coupling agent (Y8) used in the eighth aspect, there may be used,without particular limitation, any agent that can improve adhesionbetween the layer containing resin composition (X8) used in the eighthaspect and another layer containing a polar group-containing resin or aninorganic substance, such as metal, in an amount of 50 wt % or more.Suitably used are silane-, titanate-, and chromium-type coupling agents.In particular, the silane-type coupling agent (silane coupling agent) ispreferably used.

As the silane coupling agent, publicly known silane coupling agents maybe used without particular limitation. Specifically, there may bementioned n-butyltrimethoxysilane, n-butyltriethoxysilane,n-hexyltrimethoxysilane, n-hexyltriethoxysilane,n-octyltrimethoxysilane, n-octyltriethoxysilane,n-octyltripropoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(β-methoxyethoxy)silane, γ-glycidoxypropyltrimethoxysilane,γ-aminopropyltriethoxysilane, and the like.

<Organic Peroxide (Z8)>

As organic peroxide (Z8) optionally used in the eighth aspect, there maybe used, without particular limitation, publicly known organicperoxides. Specifically they include dilauroyl peroxide,1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, dibenzoyl peroxide,t-amylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,t-butylperoxy isobutyrate, t-butylperoxymaleic acid,1,1-di(t-amylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-amylperoxy)cyclohexane, t-amylperoxy isononanoate, t-amylperoxyn-octoate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-butylperoxy)cyclohexane, t-butylperoxy isopropyl carbonate,t-butylperoxy 2-ethylhexyl carbonate,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-amylperoxy benzoate,t-butylperoxy acetate, t-butylperoxy isononanoate, t-butylperoxybenzoate, 2,2-di(butylperoxy)butane, n-butyl 4,4-di(t-butylperoxy)butyrate, methyl ethyl ketone peroxide, ethyl3,3-di(t-butylperoxy)butyrate, dicumyl peroxide, t-butyl cumyl peroxide,di-t-butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide,acetylacetone peroxide, and others.

Further, the following auxiliaries may be used as necessary in theeighth aspect. Preferred examples of such auxiliary specifically includeauxiliaries for peroxy-crosslinking such as sulfur, p-quinonedioxime,p,p′-dibenzoylquinonedioxime, N-methyl-N,4-dinitrosoaniline,nitrosobenzene, diphenylguanidine, andtrimethylolpropane-N,N′-m-phenylene dimaleimide; divinylbenzene;triallyl cyanurate (TAC); triallyl isocyanurate (TRIC); and others.There may also be used multifunctional methacrylate monomers such asethylene glycol dimethacrylate, diethylene glycol dimethacrylate,polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,and allyl methacrylate; multifunctional vinyl monomers such as vinylbutyrate and vinyl stearate; and others. Among them, triallyl cyanurate(TAC) and triallyl isocyanurate (TRIC) are preferred.

In the eighth aspect, it is desirable to use the auxiliary in such anamount that the weight ratio of the auxiliary to the organic peroxide((auxiliary)/(organic peroxide)) is 1/30 to 20/1, and preferably 1/20 to10/1.

Resin composition (X8) may be crosslinked, but preferably it isnon-crosslinked. Here, “Non-crosslinked” means that the content ofcomponents insoluble in boiled xylene is 0.1 wt % or less of the wholeorganic substances present in the composition. In practice, 1.5 g of thesample is dissolved in 100 cc of p-xylene (140° C.), and after themixture is refluxed for 3 hr, insoluble components are recovered with a325-mesh screen. From the weight of dried residue of the insolublecomponents, is subtracted the weight of xylene-insoluble componentsother than polymers (for example, filler, bulking agents, pigments,etc.) to obtain “corrected final weight (Y).”

On the other hand, from the weight of the sample, is subtracted theweight of xylene-insoluble components other than polymers (for example,filler, bulking agents, pigments, etc.) to obtain “corrected initialweight (X).” Here, the content of components insoluble in boiled xyleneis determined by the following equation:

Content of components insoluble in boiled xylene (wt %)=([correctedfinal weight (Y)]÷[corrected initial weight (X)])×100

<Resin Composition (X8)>

Resin composition (X8) used in the eighth aspect containspropylene-based polymer (A8), soft propylene-based copolymer (B8), andcoupling agent (Y8). The content of (A8) is 0 to 90 wt % and preferably10 to 70 wt %, and that of (B8) is 10 to 100 wt % and preferably 30 to90 wt % (here, the total of (A8) and (B8) is 100 wt %). Desirably, thecomposition further contains coupling agent (Y8) in an amount of 0.1 to10 parts by weight, and preferably 0.5 to 5 parts by weight, relative to100 parts by weight of the composition consisting of (A8) and (B8) (thetotal amount of (A8) and (B8)), and also contains organic peroxide (Z8)in an amount of 0 to 5 parts by weight, and preferably 0 to 3 parts byweight, relative to 100 parts by weight of the composition consisting of(A8) and (B8) (the total amount of (A8) and (B8)). When composition (X8)contains organic peroxide (Z8), its amount is not less than 0.001 partsby weight and not more than 5 parts by weight, and more preferably notless than 0.01 parts by weight and not more than 3 parts by weight,relative to 100 parts by weight of the composition consisting of (A8)and (B8) (the total amount of (A8) and (B8)).

In the eighth aspect, adhesion can be attained even without organicperoxide (Z8), but adhesion would be enhanced in some cases if theorganic peroxide is used in the above range according to applications.If the amount of organic peroxide (Z8) is over the above range, themolecular weight of the resin components including propylene-basedpolymer (A8) and soft propylene-based copolymer (B8) decreases in somecases.

Resin composition (X8) is characterized in that specific softpropylene-based copolymer (B8) with the above properties is used as acomponent. Use of soft propylene-based copolymer (B8) improves thecomposition in balance of flexibility, heat resistance, andtransparency, and also provides high adhesion and high peeling strengthto other materials in a wider temperature range.

Resin composition (X8) may contain, as necessary, other resins, otherrubbers, additives such as antioxidants, heat stabilizers, weatheringstabilizers, slipping agents, anti-blocking agents, nucleating agents,pigments, and hydrochloric acid absorbers, inorganic filler, and othersas long as the performances of the composition are not impaired.

After individual components and if necessary various additives areblended, for example, with a mixer such as Henschel mixer, Banburymixer, and tumbler mixer, the blend may be molded, with a single-screwor twin-screw extruder, into pellets, which are then supplied to apublicly known molding machine. Alternatively, the blend prepared asabove may be supplied to a publicly known molding machine such as sheetmolding machine and injection molding machine.

The heat resistance (TMA) of resin composition (X8) is 100° C. orhigher, and preferably 110 to 130° C. The tensile strength at break ofresin composition (X8) is 8 to 25 MPa, and preferably 10 MPa to 25 MPa,and its modulus in tension is 5 to 50 MPa, and preferably 10 to 35 MPa.

It is desirable that resin composition (X8) has, additionally andindependently, the following properties. Resin composition (X8) may haveeach of the properties independently, but would be more preferable withthese properties at the same time.

(i) In the dynamic viscoelastic measurement at torsion mode (10 rad/s),the loss tangent (tan δ) peak appears in the range of −25° C. to 25° C.,and the loss tangent is 0.5 or more;(ii) the ratio of storage modulus G′(20° C.) to G′(100° C.) (G′(20°C.)/G′(100° C.)) determined based on the above dynamic viscoelasticmeasurement is 5 or less; and(iii) the residual strain is 20% or less when a specimen is elongated by100% at a tensile speed of 30 mm/min with a chuck-to-chuck distance of30 mm, kept for 10 min, and freed from the load, and the strain ismeasured after 10 min.

In a desirable embodiment in terms of (i), the loss tangent, tan δ, is0.5 or more, preferably 0.5 to 2.5, and more preferably 0.6 to 2 in −25°C. to 25° C. When tan δ is 0.5 or less, the flexibility may beinsufficient, or even through flexibility is attained, scratchresistance tends to be poor.

In a desirable embodiment in terms of (ii), the ratio of storage modulusG′(20° C.) to G′(100° C.) (G′(20° C.)/G′(100° C.)) is 5 or less,preferably 4 or less, and more preferably 3.5 or less. When G′(20°C.)/G′(100° C.) exceeds 5, the surface may suffer from stickiness or thelike, possibly resulting in poor handleability or inadequate heatresistance.

In a desirable embodiment in terms of (iii), the residual strain is 20%or less, preferably 18% or less, and more preferably 16% or less, when adumbbell specimen of 1 mm thick, 50 mm long, and 5 mm wide is elongatedby 100% at a tensile speed of 30 mm/min with a chuck-to-chuck distanceof 30 mm, kept for 10 min, and freed from the load, and the strain ismeasured after 10 min. If the residual strain exceeds 20%, rubberelasticity is likely to decrease, possibly making it difficult to use insuch applications where stretching property and resilience are required.

It is desirable that a molded article made of resin composition (X8) hasan internal haze of 25% or less, and preferably 20% or less as measuredat a thickness of 1 mm.

It is also desirable that a molded article made of resin composition(X8) has a Young's modulus in tension (YM) of 100 MPa or less, andpreferably 80 MPa or less as measured in accordance with JIS K 6301.

The melt flow rate (measured in accordance with ASTM D1238, at 230° C.under a load of 2.16 kg) of resin composition (X8) is generally 0.0001to 1000 g/10 min, preferably 0.0001 to 900 g/10 min, and more preferably0.0001 to 800 g/10 min. The intrinsic viscosity [n] of resin composition(X8) measured at 135° C. in decahydronaphthalene is generally 0.01 to 10dl/g, preferably 0.05 to 10 dl/g, and more preferably 0.1 to 10 dl/g.

It is preferred that in the endothermic curve for resin composition (X8)obtained with a differential scanning calorimeter (DSC), the temperatureat maximum endothermic peak, which corresponds to the melting point (Tm,° C.), is observed at 100° C. or higher, and the melting endothermicentalpy corresponding to the peak is preferably in the range of 5 to 40J/g, and more preferably 5 to 35 J/g.

The temperature at maximum endothermic peak (melting point) of resincomposition (X8) is 130° C. or higher, preferably 140° C. or higher, andmore preferably 160° C. or higher.

The melt tension (MT) of resin composition (X8) is generally 0.5 to 10g, and preferably 1 to 10 g. With this range of MT, the composition isreadily molded into film, sheet, tube, and the like. Here, the melttension (MT) is determined with a melt tension tester (available fromToyo Seiki Seisaku-sho, Ltd.) as the tension applied on a filament whenthe composition is extruded into a strand at a rate of 15 mm/min at 200°C. and the strand is drawn at a constant speed (10 m/min).

<Laminate>

A laminate usable in various applications can be obtained by laminatinga layer [a] containing resin composition (X8) and another layer [b]containing a certain material (base material).

There is no particular limitation on the method for producing thelaminate. For instance, the laminate is obtained by a method in whichresin composition (X8) is molded with the above conventional moldingmachine such as sheet molding machine and injection molding machine andthe resultant molding is heat-bonded with a base material with a heatroller or by vacuum molding. Alternatively, the laminate may be producedby melt-extruding resin composition (X8) on a base material. As long asthe effects of the eighth aspect are not impaired, an adhesive layer maybe provided between the molded article made of resin composition (X8)and the base material layer, but in the eighth aspect, sufficientadhesion strength can be obtained without the adhesive layer. When noadhesive layer is provided, the laminate of the eighth aspect isexcellent in flexibility, rubber elasticity, and transparency, and theproduction process is simplified.

As the base material for the laminate of the eighth aspect, a polarmaterial is used. Specifically, there may be mentioned metal (aluminum,copper, stainless steel, iron, and other known metallic base materials),inorganic compounds (glass and other known inorganic base materials),polar plastics (AS (acrylonitrile/styrene) resin, ABS(acrylonitrile/butadiene/styrene) resin, polyvinyl chloride resin,fluororesin, polyester resin such as polyethylene terephthalate andpolyethylene naphthalate, phenol resin, polyacrylic resin, polyamideresin including various kinds of nylons, polyimide resin,polyamide-imide resin, polyurethane resin, polycarbonate resin, andother known polar plastics), and others.

The laminate of the eighth aspect is used for automobile materials,electrical/electronics materials, construction materials (including wallcovering and window materials), convenience goods (includingstationery), materials for transportation, civil engineering, andbuilding, and food packaging.

9. Ninth Aspect

Hereinafter, the ninth aspect of the present invention is explained indetail.

<Propylene-Based Polymer (A9)>

Propylene-based polymer (A9) used in the ninth aspect is the same aspropylene-based copolymer (A8) used in the eighth aspect.

Propylene-based polymers (A9) used in the ninth aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. The C₂-C₂₀ α-olefins except propylene includeethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,1-eicosene, and others. Ethylene or a C₄-C₁₀ α-olefin is preferable.

These α-olefins may form a random or block copolymer with propylene.

The structural units derived from these α-olefins may be contained in anamount of 35 mol % or less and preferably 30 mol % or less in thepolypropylene.

It is desirable that the melt flow rate (MFR) of propylene-based polymer(A9), as measured at 230° C. under a load of 2.16 kg in accordance withASTM D1238, is 0.01 to 10000 g/10 min, and preferably 0.05 to 100 g/10min.

The melting point of propylene-based polymer (A9) measured with adifferential scanning calorimeter is 100° C. or higher, preferably 100to 160° C., and more preferably 110 to 150° C.

Propylene-based polymer (A9) may be either isotactic or syndiotactic,but the isotactic one is preferred considering heat resistance andothers.

There may be used, if necessary, a plurality of propylene-based polymers(A9), for example, two or more components different in melting point orrigidity.

To obtain desired properties, there may be used, as propylene-basedpolymer (A9), one polymer or a combination of polymers selected fromhomopolypropylene excellent in heat resistance (known homopolypropylene,generally containing 3 mol % or less of copolymerized components exceptpropylene), block polypropylene excellent in balance of heat resistanceand flexibility (known block polypropylene, generally containing 3 to 30wt % of n-decane-soluble rubber components), and random polypropyleneexcellent in balance of flexibility and transparency (known randompolypropylene, generally having a melting peak of 100° C. or higher andpreferably 110° C. to 150° C. as measured with a differential scanningcalorimeter DSC).

Such propylene-based polymer (A9) can be produced, for example, likeisotactic polypropylene (A1) used in the first aspect, by polymerizingpropylene or copolymerizing propylene and the α-olefin with Zieglercatalyst that is composed of a solid catalyst component containingmagnesium, titanium, halogen, and an electron donor as essentialcomponents, an organoaluminum compound, and an electron donor, or ametallocene catalyst containing a metallocene compound as one componentof the catalyst.

<Soft Propylene-Based Copolymer (B9)>

Soft propylene-based copolymer (B9) used in the ninth aspect is acopolymer of propylene and at least one C₂-C₂₀ α-olefin exceptpropylene, and its Shore A hardness is 30 to 80, and preferably 35 to70, and its melting point is lower than 100° C. or not observed whenmeasured with a differential scanning calorimeter DSC. Here, “meltingpoint is not observed” means that any melting endothermic peak ofcrystal having a melting endothermic enthalpy of crystal not less than 1J/g is not observed in the temperature range of −150 to 200° C. Themeasurement conditions are as described in Examples of the ninth aspect.

In soft propylene-based copolymer (B9), the α-olefin used as theco-monomer is preferably ethylene and/or a C₄-C₂₀ α-olefin.

In soft propylene-based copolymer (B9), the content of propylene-derivedstructural units is 45 to 92 mol % and preferably 56 to 90 mol %, andthe content of structural units derived from the α-olefin used as theco-monomer is 8 to 55 mol %, and preferably 10 to 44 mol %.

It is desirable that the melt flow rate (MFR) of propylene polymer (B9),as measured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238, is 0.01 to 100 g/10 min, and preferably 0.05 to 50 g/10 min.

There is no particular limitation on the method for producing softpropylene-based copolymer (B9). There may be mentioned methods similarto those for producing soft propylene-based polymer (B8) used in theeighth aspect.

Namely, soft propylene copolymer (B9) can be produced by polymerizingpropylene or copolymerizing propylene and the α-olefin in the presenceof a publicly known catalyst used for stereospecific olefinpolymerization that can yield an isotactic or syndiotactic polymer, forexample, a catalyst mainly composed of a solid titanium component and anorganometallic compound, or a metallocene catalyst containing ametallocene compound as one of catalyst components. Preferably, asdescribed later, the copolymer is produced by copolymerizing propylene,ethylene, and a C₄-C₂₀ α-olefin in the presence of the metallocenecatalyst.

It is preferred that soft propylene-based copolymer (B9) haveadditionally independently the following properties.

Soft propylene-based copolymer (B9) preferably has the same propertiesas propylene/ethylene/α-olefin copolymer (B1) used in the first aspectconcerning triad tacticity (mm-fraction), stress at 100% elongation,crystallinity, glass transition temperature Tg, and molecular weightdistribution (Mw/Mn). These properties provide the same effects.

For instance, the triad tacticity (mm-fraction) of soft propylene-basedcopolymer (B9) determined by ¹³C-NMR is preferably 85% or more, morepreferably 85 to 97.5%, still more preferably 87% to 97%, andparticularly preferably 90% to 97%. With the above range of triadtacticity (mm-fraction), in particular, excellent balance of flexibilityand mechanical strength is attained, which is desirable for the presentinvention. The mm-fraction can be determined by the method described inWO 2004/087775 from Page 21 line 7 to Page 26 line 6.

The stress at 100% elongation (M100) of soft propylene-based copolymer(B9) is generally 4 MPa or less, preferably 3 MPa or less, and morepreferably 2 MPa or less, as measured in accordance with JIS K6301 at aspan of 30 mm and a tensile speed of 30 mm/min at 23° C. with a JIS #3dumbbell. With the above range of M100, soft propylene-based polymer(B9) provides excellent flexibility, transparency, and rubberelasticity.

The crystallinity of soft propylene-based copolymer (B9) is generally20% or less, and preferably 0 to 15% as measured by X-raydiffractometry. It is also desirable that the soft propylene-basedcopolymer in the present invention has a single glass transitiontemperature and that the glass transition temperature Tg is generally−10° C. or lower, and preferably −15° C. or lower as measured with adifferential scanning calorimeter (DSC). With the above range of glasstransition temperature Tg, soft propylene-based copolymer (B9) providesexcellent cold temperature resistance and low-temperature properties.

The molecular weight distribution (Mw/Mn, relative to polystyrenestandards, Mw: weight-average molecular weight, Mn: number-averagemolecular weight) of soft propylene-based copolymer (B9) is preferably4.0 or less, more preferably 3.0 or less, and still more preferably 2.5or less as measured by GPC.

When soft propylene copolymer (B9) shows a melting point (Tm in ° C.) inthe endothermic curve obtained with a differential scanning calorimeter(DSC), the melting endothermic entalpy AH is 30 J/g or less and thefollowing relation is satisfied between C₃ content (mol %) and meltingendothermic entalpy ΔH (J/g):

ΔH<345 Ln(C ₃ content in mol %)−1492,

wherein, 76≦C₃ content (mol %)≦90.

Preferred specific examples of soft propylene-based copolymer (B9)include propylene/ethylene/α-olefin copolymer (B9-1) below. Whenpropylene/ethylene/α-olefin copolymer (B9-1) is used, there is provideda solar cell-sealing sheet with excellent flexibility, heat resistance,mechanical strength, solar cell-sealing performance, and transparency.Here, “solar cell-sealing performance” means the ability of reducing theincidence of cracking of solar cell elements, due to the excellentflexibility, on embedding the elements.

In propylene/ethylene/α-olefin copolymer (B9-1), the content ofpropylene-derived structural units is 45 to 92 mol %, preferably 56 to90 mol %, and more preferably 61 to 86 mol %;

the content of ethylene-derived structural units is 5 to 25 mol %,preferably 5 to 14 mol %, and more preferably 8 to 14 mol %; and thecontent of C₄-C₂₀ α-olefin-derived structural units is 3 to 30 mol %,preferably 5 to 30 mol %, and more preferably 6 to 25 mol %. 1-Butene isparticularly preferred as the α-olefin.

Propylene/ethylene/α-olefin copolymer (B9-1) containingpropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀ α-olefin-derived structural units in the above ratio has goodcompatibility with propylene-based polymer (A9), providing a solarcell-sealing sheet with adequate transparency, flexibility, heatresistance, and scratch resistance.

<Thermoplastic Resin Composition Used for Solar Cell-Sealing Sheet, andSolar Cell-Sealing Sheet>

The solar cell-sealing sheet of the ninth aspect is a solar cell-sealingsheet (also called “sheet-shaped sealing material for solar cells”)formed from thermoplastic resin composition (X9) containing (A9) and(B9) below in amounts described below:

propylene-based polymer (A9) in an amount of 0 to 70 parts by weight,and preferably 10 to 50 parts by weight; and

soft propylene-based copolymer (B9) in an amount of 30 to 100 parts byweight, and preferably 50 to 90 parts by weight, wherein the total of(A9) and (B9) is 100 parts by weight.

As described above, with the preferred ranges of (A9) and (B9),composition (X9) is nicely molded into sheets and resultant solarcell-sealing sheets are excellent in heat resistance, transparency, andflexibility, which is suitable for the ninth aspect.

In the solar cell-sealing sheet of the ninth aspect, there may be usedcoupling agent (Y9) to promote adhesion of (A9) and (B9) to glass,plastics, or the like. There is no particular limitation on couplingagent (Y9) as long as it can improve adhesion between the layercontaining resin composition (X9) and another layer containing 50 wt %or more of polar group-containing resin or inorganic substance such asmetal. Suitably used coupling agents are of silane-type, titanate-type,or chromium-type. In particular, a silane-type coupling agent (silanecoupling agent) is preferably used.

As the above silane coupling agent, publicly known agents may be usedwithout particular limitation. Specifically they includevinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(β-methoxyethoxysilane), γ-glycidoxypropyltrimethoxysilane,γ-aminopropyltriethoxysilane, and the like.

It is desirable that the silane coupling agent is contained in an amountof 0.1 to 5 parts by weight, and preferably 0.1 to 3 parts by weight,relative to 100 parts by weight of thermoplastic resin composition (X9)(the total amount of (A9) and (B9)).

The above coupling agent may be grafted to thermoplastic resincomposition (X9) using organic peroxide (Z9). In this case, it isdesirable that the silane coupling agent is present in an amount from0.1 parts to 5 parts by weight relative to 100 parts by weight ofthermoplastic resin composition (X9) (the total amount of (A9) and(B9)). Thermoplastic resin composition (X9) silane-grafted also providesthe same or more adhesion to glass and plastics as compared with a blendcontaining the silane coupling agent. The amount of organic peroxide(Z9), if used, is preferably 0.001 to 5 parts by weight, and morepreferably 0.01 to 3 parts by weight, relative to 100 parts by weight ofthermoplastic resin composition (X9) (the total amount of (A9) and(B9)).

As organic peroxide (Z9), there may be used publicly known organicperoxides, including those which is the same as organic peroxide (Z8)used in the eighth aspect, without particular limitation.

Specifically, organic peroxides (Z9) include dilauroyl peroxide,1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, dibenzoyl peroxide,t-amylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,t-butylperoxy isobutyrate, t-butylperoxymaleic acid,1,1-di(t-amylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-amylperoxy)cyclohexane, t-amylperoxy isononanoate, t-amylperoxyn-octoate, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di(t-butylperoxy)cyclohexane, t-butylperoxy isopropyl carbonate,t-butylperoxy 2-ethylhexyl carbonate,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-amylperoxy benzoate,t-butylperoxy acetate, t-butylperoxy isononanoate, t-butylperoxybenzoate, 2,2-di(butylperoxy)butane, n-butyl4,4-di(t-butylperoxy)butyrate, methyl ethyl ketone peroxide, ethyl3,3-di(t-butylperoxy)butyrate, dicumyl peroxide, t-butyl cumyl peroxide,di-t-butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide,acetylacetone peroxide, and the like.

In the ninth aspect, the following auxiliary may be further used asnecessary. As such auxiliary, preferably used are the same auxiliariesas those used in the eighth aspect.

Specifically, preferred auxiliaries include auxiliaries forperoxy-crosslinking such as sulfur, p-quinonedioxime,p,p′-dibenzoylquinonedioxime, N-methyl-N,4-dinitrosoaniline,nitrosobenzene, diphenylguanidine, andtrimethylolpropane-N,N′-m-phenylene dimaleimide; divinylbenzene;triallyl cyanurate (TAC); and triallyl isocyanurate (TAIC). As theauxiliary, there may be also used multifunctional methacrylate monomerssuch as ethylene glycol dimethacrylate, diethylene glycoldimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropanetrimethacrylate, and allyl methacrylate; multifunctional vinyl monomerssuch as vinyl butyrate and vinyl stearate; and others. Among them,triallyl cyanurate (TAC) and triallyl isocyanurate (TRIC) are preferred.

In the ninth aspect, the desirable weight ratio of the auxiliary to theorganic peroxide ((auxiliary)/(organic peroxide)) is 1/30 to 20/1, andpreferably 1/20 to 10/1.

Thermoplastic resin composition (X9) used in the ninth aspect may becrosslinked, but preferably it is non-crosslinked. Here,“non-crosslinked” means that the content of component insoluble inboiled xylene is 0.1 wt % or less in the whole organic substancespresent in the composition. Specifically, the content of componentinsoluble in boiled xylene is determined in a similar manner to thatdescribed in the eighth aspect.

Namely, in practice, 1.5 g of the sample is dissolved in 100 cc ofp-xylene (140° C.), which is then refluxed for 3 hr, and insolublecomponents are recovered with a 325-mesh screen. From the weight ofdried residue of the insoluble component, is subtracted the weight ofthe xylene-insoluble components other than polymer components (forexample, filler, bulking agents, pigments, etc.) to obtain “correctedfinal weight (Y).”

On the other hand, from the weight of the sample, is subtracted theweight of the xylene-insoluble components other than polymer components(for example, filler, bulking agents, pigments, etc.) to obtain“corrected initial weight (X).”

Here, the content of component insoluble in boiled xylene is determinedby the following equation:

Content of component insoluble in boiled xylene (wt %)=([corrected finalweight (Y)]÷[corrected initial weight (X)])×100.

The solar cell-sealing sheet of the ninth aspect also contains variousother additives, which include, for example, ultraviolet absorbers andlight stabilizers for preventing degradation caused by ultraviolet raysin the sun light, antioxidants, and others.

As the ultraviolet absorbers, there are used specifically benzophenonessuch as 2-hydroxy-4-methoxybenzophenone,2,2-dihydroxy-4-methoxybenzophenone,2-hydroxy-4-methoxy-4-carboxybenzophenone, and2-hydroxy-4-(n-octyloxy)benzophenone; benzotriazoles such as2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole and2-(2-hydroxy-5-methylphenyl)benzotriazole; and salicylate esters such asphenyl salicylate and p-octylphenyl salicylate.

As the light stabilizers, hindered amines are used.

As the antioxidants, hindered phenols and phosphites are used.

The sheet of the ninth aspect is obtained from a sheet made ofthermoplastic resin composition (X9) having a thickness of 0.1 to 3 mm.If the thickness is below this range, glass or solar cells may bedamaged in the lamination step. If the thickness is over this range, thelight transmittance lowers, whereby the photovoltaic power generationpossibly lowers.

The methods for molding the solar cell-sealing sheet relating to theninth aspect, although not particularly limited to, include publiclyknown extrusion molding (cast molding, extrusion sheet molding,inflation molding, injection molding, etc.), compression molding,calendar molding, and others. The sheet may be embossed. Surfaceembossing is preferred since mutual blocking of sheets is suppressed andthe embossed surface serves as a cushion for glass and solar cells toprevent damage on lamination.

For resin composition (X9) forming the solar cell-sealing sheet, theinternal haze is preferably 1.0% to 10%, and more preferably 1.5% to 7%when molded into a 1-mm thick press-molded sheet.

The internal haze of the solar cell-sealing sheet of the ninth aspect is1.0% to 10%, and preferably 1.5% to 7%. Note that, in this case, theinternal haze is measured with the solar cell-sealing sheet irrespectiveof its thickness.

The light transmittance (Trans) of resin composition (X9) is 88% ormore, and preferably 90% or more when molded into a 1-mm thickpress-molded sheet.

The light transmittance of the solar cell-sealing sheet of the ninthaspect is 88% or more, and preferably 90% or more. Note that, in thiscase, the light transmission is measured with the solar cell-sealingsheet irrespective of its thickness.

The heat resistance (TMA) of resin composition (X9) is preferably 80° C.or higher, and more preferably 90 to 130° C. when molded into a 2-mmthick press-molded sheet.

The tensile strength at break of resin composition (X9) is preferably 8to 25 MPa, and more preferably 10 to 25 MPa, and modulus in tensionthereof is preferably 5 to 50 MPa, more preferably 10 to 35 MPa, andstill more preferably 10 to 30 MPa.

It is desirable that the solar cell-sealing sheet of the ninth aspect orresin composition (X9) forming the solar cell-sealing sheet hasadditionally independently the following properties. The followingproperties each may be satisfied independently, but in more preferableembodiments, these are satisfied at the same time.

(i) In the dynamic viscoelastic measurement at torsion mode (10 rad/s),the loss tangent (tan δ) peak appears in the range of −25° C. to 25° C.,and the loss tangent is 0.5 or more;(ii) the ratio of storage modulus G(20° C.) to G′(100° C.) (G′(20°C.)/G′(100° C.)) determined based on the above dynamic viscoelasticmeasurement is 5 or less; and(iii) the residual strain is 20% or less when a specimen is elongated by100% at a tensile speed of 30 mm/min with a chuck-to-chuck distance of30 mm, kept for 10 min, and freed from the load, and the strain ismeasured after 10 min.

In a desirable embodiment in terms of (i), the loss tangent, tan δ, is0.5 or more, preferably 0.5 to 2.5, and more preferably 0.6 to 2 in −25°C. to 25° C. When tan δ is 0.5 or less, the flexibility may beinsufficient, or even through flexibility is attained, scratchresistance tends to be poor.

In a desirable embodiment in terms of (ii), the ratio of storage modulusG′(20° C.) to G′(100° C.) (G′(20° C.)/G′(100° C.)) is 5 or less,preferably 4 or less, and more preferably 3.5 or less. When G′(20°C.)/G′(100° C.) exceeds 5, the surface may suffer from stickiness or thelike, possibly resulting in poor handleability or inadequate heatresistance.

In a desirable embodiment in terms of (iii), the residual strain is 20%or less, preferably 18% or less, and more preferably 16% or less, when adumbbell specimen of 1 mm thick, 50 mm long, and 5 mm wide is elongatedby 100% at a tensile speed of 30 mm/min with a chuck-to-chuck distanceof 30 mm, kept for 10 min, and freed from the load, and the strain ismeasured after 10 min. If the residual strain exceeds 20%, rubberelasticity is likely to decrease, and moldability tends to be poor.

It is desirable that resin composition (X9) has the same properties asresin composition (X8) used in the eighth aspect concerning melt flowrate, intrinsic viscosity [n], melting point (Tm, ° C.) and meltingendothermic entalpy.

Namely, the melt flow rate (measured in accordance with ASTM D1238 at230° C. under a load of 2.16 kg) of resin composition (X9) is generally0.0001 to 1000 g/10 min, preferably 0.0001 to 900 g/10 min, and morepreferably 0.0001 to 800 g/10 min, and its intrinsic viscosity [η]measured in decahydronaphthalene at 135° C. is generally 0.01 to 10dl/g, preferably 0.05 to 10 dl/g, and more preferably 0.1 to 10 dl/g.

Preferably, in the endothermic curve of resin composition (X9) obtainedwith a differential scanning calorimeter (DSC), the temperature atmaximum endothermic peak, which corresponds to the melting point (Tm, °C.), is observed at 100° C. or higher and the melting endothermicentalpy corresponding to the peak is in the range of 5 to 40 J/g, andmore preferably 5 to 35 J/g.

The temperature at maximum endothermic peak (melting point) of resincomposition (X9) is 100° C. or higher, preferably 110° C. or higher, andmore preferably 120° C. or higher.

The melt tension (MT) of resin composition (X9) is generally 0.5 to 10g, and preferably 1 to 10 g. With this range of MT, the solarcell-sealing sheet can be molded excellently. Here, the melt tension(MT) is determined with a melt tension tester (available from Toyo SeikiSeisaku-sho, Ltd.) as the tension applied on a filament when thecomposition is extruded into a strand at a rate of 15 mm/min at 200° C.and the strand is draw at a constant speed (10 m/min).

Thermoplastic resin composition (X9) may contain other resins, otherrubbers, and inorganic filler, as long as the objectives of the ninthaspect are not impaired.

The solar cell-sealing sheet of the ninth aspect can be used in a solarcell in which said sheet is laminated on the one side and/or both sidesof a solar cell element, and if necessary, a surface-protective layer isfurther laminated on the outer face of the solar cell-sealing sheet(s).FIG. 9-1 shows one embodiment in which the solar cell-sealing sheet isapplied.

The methods for producing solar cells are not particularly limited butinclude, for instance, a method in which a surface-protective layer, asolar cell element, and the solar cell-sealing sheet of the ninth aspectare successively laminated, and they are hot-press laminated by vacuumsuction or the like.

For the surface protective layer, publicly known materials may be usedwithout particular limitation as long as the layer can protect the solarcell and solar cell-sealing sheet layer without impairing the objectivesof the solar cell. Specific examples of material used for the surfaceprotective layer include glass, polyethylene resin, polypropylene resin,polycycloolefin resin, AS (acrylonitrile/styrene) resin, ABS(acrylonitrile/butadiene/styrene) resin, polyvinyl chloride resin,fluororesin, polyester resin such as polyethylene terephthalate andpolyethylene naphthalate, phenol resin, polyacrylic resin, polyamideresin including various nylons, polyimide resin, polyamide-imide resin,polyurethane resin, cellulose resin, silicone resin, polycarbonateresin, and the like. A plurality of these resins may be used. There mayalso be preferably used an inorganic/organic composite film in which aninorganic oxide or the like is deposited on such resin for improvingperformances as gas and/or moisture barrier.

Between the surface protective layer and the layer of solar cell-sealingsheet of the ninth aspect or between a plurality of surface protectivelayers, a layer of publicly known adhesive or adhesive resin may beinterposed to enhance the adhesion. According to the mode of using thesolar cell, one side of the surface protective layer may havelight-shielding and/or light-reflecting nature.

Applications of the ninth aspect include a solar cell module fabricatedby using the solar cell-sealing sheet of the ninth aspect and anelectric power generator having said solar cell module. As theconfigurations of the solar cell module and electric power generator,there may be mentioned the configurations in which the solarcell-sealing sheet of the ninth aspect is used instead of the solarcell-sealing sheet of the tenth aspect in the configurations of thesolar cell module and electric power generator of the tenth aspectdescribed later. As components other than the solar cell-sealing sheetused for the solar cell module, for example, a front protective sheetfor solar cell modules, a back protective sheet for solar cell modules,a solar cell element, there may be used the same components as those inthe tenth aspect described later.

10. Tenth Aspect

Hereinafter, the tenth aspect of the present invention is explained indetail.

The tenth aspect of invention provides to an electrical/electronicelement-sealing sheet having layer (I-10) made of an ethylene-basedcopolymer, in which the Shore A hardness is 50 to 90 and ethylenecontent is 60 to 95 mol %, and layer (II-10) made of thermoplastic resincomposition (X10). The composition contains 0 to 90 parts by weight ofpropylene-based polymer (A10) whose melting point is 100° C. or higheras measured with a differential scanning calorimeter, and 10 to 100parts by weight of propylene-based copolymer (B10) that is a copolymerof propylene and at least one olefin selected from ethylene and C₄-C₂₀α-olefins, in which the Shore A hardness is 30 to 80 and the meltingpoint is lower than 100° C. or not observed when measured with adifferential scanning calorimeter (wherein, the total of (A10) and (B10)is 100 parts by weight).

The tenth aspect of invention is explained in detail below.

<Layer (I-10) Made of Ethylene-Based Copolymer> [Ethylene-BasedCopolymer]

The ethylene-based copolymer used for layer (I-10) of the tenth aspectis obtained by copolymerizing ethylene and at least one monomer exceptethylene, has a Shore A hardness of 50 to 90, and contains 60 to 95 mol% of ethylene-derived structural units.

With the above range of Shore A hardness, cracking of solar cells insealing can be suppressed, which is preferred. The Shore A hardness ispreferably 55 to 88, and more preferably 60 to 85. Shore A hardness canbe measured in accordance with JIS K6301.

The above range of ethylene content is preferred, since such copolymercan readily attain the Shore A hardness in the above range. The ethylenecontent is preferably 65 to 92 mol %, and more preferably 70 to 90 mol%. The ethylene content is determined by quantifying the ratio ofindividual monomer units based on ¹³C-NMR spectrum.

In the ethylene-based copolymer used for layer (I-10), any monomersexcept ethylene may be used without particular limitation as long as thecopolymer satisfy the above conditions on the hardness and ethylenecontent. Therefore, various monomers copolymerizable with ethylene maybe used as appropriate, but it is desirable to use at least one monomerselected from vinyl acetate, acrylic esters, methacrylic esters,propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Thesemonomers may be used alone or in combination of two or more. There is noparticular limitation on the combination when two or more monomers areused.

Among these, vinyl acetate, propylene, and/or 1-butene are preferablyused as a co-monomer because the resulting ethylene-based copolymer hasexcellent transparency, flexibility, and others. Consequently, theethylene-based copolymer is particularly preferably ethylene/vinylacetate copolymer, ethylene/propylene copolymer, or ethylene/butenecopolymer.

[Ethylene/Vinyl Acetate Copolymer]

In ethylene/vinyl acetate copolymer (EVA) preferably used in the tenthaspect, it is desired that the content of vinyl acetate (VA)-derivedstructural units is 5 to 40 wt %, and preferably 10 to 35 wt %. Withthis range of VA content, the resulting resin has excellent balance ofweather resistance, flexibility, transparency, mechanical properties,and film-forming performance.

The melt flow rate (MFR2.16) (measured in accordance with ASTM D1238 at190° C. under a load of 2.16 kg) of ethylene/vinyl acetate copolymer isdesirably 0.1 to 50 g/10 min, and preferably 1 to 30 g/10 min.

In layer (I-10), there may be used one ethylene/vinyl acetate copolymer,or two or more ethylene/vinyl acetate copolymers different in molecularweight, or the like.

[Ethylene/Propylene Copolymer or Ethylene/Butene Copolymer]

The ethylene/propylene copolymer or ethylene/butene copolymer preferablyused in the tenth aspect is a copolymer of ethylene with propyleneand/or butene, and generally a non-crystalline or low-crystalline randomcopolymer.

This ethylene/propylene copolymer or ethylene/butene copolymer desirablyhas a melt flow rate (MFR2.16) (measured in accordance with ASTM D1238,at 190° C. under a load of 2.16 kg) of 0.1 g/10 min to 50 g/10 min,preferably 1 g/10 min to 30 g/10 min, and more preferably 5 g/10 min to25 g/10 min. With this range of melt flow rate, the copolymer provideselectrical/electronics element-sealing sheets excellent in flexibilitywith high productivity.

The density of such ethylene/propylene copolymer or ethylene/butenecopolymer (measured in accordance with ASTM D1505) is generally 855 to905 kg/m³, preferably 857 to 895 kg/m³, and more preferably 858 to 890kg/m³. This range of density nearly corresponds to the above ethylenecontent at which preferable properties are attained.

For this ethylene/propylene copolymer or ethylene/butene copolymer, theratio of melt flow rate measured at 190° C. under a load of 10 kg(MFR10) (measured in accordance with ASTM D1238) to MFR2.16(MFR10/MFR2.16) is preferably 5 to 12.

Desirably, the molecular weight distribution (Mw/Mn) ofethylene/propylene copolymer or ethylene/butene copolymer is 1.5 to 3.0,and preferably 1.8 to 2.5 as measured by gel permeation chromatography(GPC). With the above range of molecular weight distribution (Mw/Mn),the copolymer provides sheets with reduced stickiness after molded.

The crystallinity of such ethylene/propylene copolymer orethylene/butene copolymer is generally 40% or less, and preferably 10%to 30% as measured by X-ray diffractometry.

The ethylene/propylene copolymer or ethylene/butene copolymer asdescribed above can be produced by conventional methods in which atitanium catalyst, a vanadium catalyst, or a metallocene catalyst (forexample, metallocene catalyst described in WO 97/10295) is used.

Silane Coupling Agent (Y10)

Ina desirable embodiment of the tenth aspect, layer (I-10) furthercontains 0.1 to 5 parts by weight of silane coupling agent (Y10), 0 to 5parts by weight of organic peroxide (Z10), and 0 to 5 parts by weight ofa weathering stabilizer relative to 100 parts by weight of theethylene-based copolymer.

The main objective of blending coupling agent (Y10) is generally toenhance adhesion to glass, plastics, and others.

As coupling agent (Y10), there may be used, without particularlimitations, any coupling agent that can enhance adhesion of layer(I-10) to another layer made of glass, polyester resin, or the like.Preferably used are silane-type coupling agents, titanate-type couplingagents, or chromium-type coupling agents. Particularly, silane-typecoupling agents (silane coupling agent) are preferably used.Conventional silane coupling agents may be used without particularlimitation, specifically including the same silane coupling agents asthose used in the ninth aspect.

The amount of the silane coupling agent to be added is typically 0.1 to5 parts by weight, and preferably 0.1 to 3 parts by weight relative to100 parts by weight of the ethylene-based copolymer. Adding the couplingagent in the above ratio is preferred since it provides sufficientlyimproved adhesion without adverse influence on the transparency andflexibility of the resultant film.

[Radical Initiator]

For the coupling agents, including silane coupling agents asrepresentatives, the improving effects on adhesion to glass is enhancedwhen the agent is grafted to the ethylene-based copolymer using aradical initiator. As the radical initiator preferably used in the tenthaspect, there may be used, without particular limitation, any radicalinitiators that can graft the ethylene-based copolymer with the couplingagent. Above all, organic peroxide (Z10) is particularly preferred asthe radical initiator.

The amount of organic peroxide (Z10) added herein is preferably 0 to 5parts by weight relative to 100 parts by weight of the ethylene-basedcopolymer. The content of organic peroxide (Z10), if any, is preferably0.001 to 5 parts by weight and more preferably 0.01 to 3 parts by weightrelative to 100 parts by weight of the ethylene-based copolymer.

As organic peroxide (Z10), publicly known organic peroxides may be usedwithout particular limitation, but preferred specific examples includeperoxides like organic peroxide (Z8) used in the eighth aspect.

[Weathering Stabilizer]

Layer (I-10) may further contain various weathering stabilizers.Preferred amount of the weathering stabilizer present in layer (I-10) is0 to 5 parts by weight relative to 100 parts by weight of theethylene-based copolymer. For example, the content of weatheringstabilizer, if any, is preferably 0.01 to 5 parts by weight relative to100 parts by weight of the ethylene-based copolymer. Adding theweathering stabilizer in the above ratio assures sufficient improvingeffects on weathering stability and suppresses deterioration in thetransparency and adhesion to glass of layer (I-10).

As the weathering stabilizer, there may be used one or more compoundsselected from ultraviolet absorbers, light stabilizers, antioxidants,and the like.

As the ultraviolet absorber, light stabilizer, and antioxidant,specifically, there may be mentioned those used in the ninth aspect.

[Other Components]

Layer (I-10) may optionally contain various components besides the abovecomponents, as long as the objectives of the tenth aspect are notimpaired. For instance, it may contain as appropriate, polyolefins otherthan the above ethylene-based copolymer, resins and/or rubbers otherthan polyolefins, and one or more additives selected from plasticizers,filler, pigments, dyes, antistatic agents, antibacterial agents,fungicides, flame retardants, dispersants, and others.

[Composition and Formation Method of Layer (I-10)]

The thickness of layer (I-10) is generally 10 μm to 1000 μm andpreferably 20 μm to 600 μm. With this range of thickness, the layer hassufficient adhesion strength to glass and also assures sufficient lighttransmittance that contributes generation of high photovoltaic power.

As the method for forming layer (I-10), there may be employed, althoughnot limited to, conventional extrusion molding (cast molding, extrusionsheet molding, inflation molding, injection molding, etc.), compressionmolding, calendar molding, and the like. In the tenth aspect, preferredis a method in which layer (I-10) and layer (II-10) made ofthermoplastic resin composition (X10) described later are co-extrudedwith a publicly known melt-extrusion machine such as cast moldingmachine, extrusion sheet molding machine, inflation molding machine, andinjection molding machine, to obtain a laminate; or a method in whichthermoplastic resin composition (X10) is molded into layer (II-10), onwhich layer (I-10) is applied as melt or hot-laminated to obtain alaminate.

For the desirable composition forming layer (I-10), the internal haze is0.1% to 15%, and preferably 0.1% to 10% as measured with a 0.5-mm thickspecimen.

<Layer (II-10) Made of Thermoplastic Resin Composition (X10)>[Thermoplastic Resin Composition (X10)]

Layer (II-10) used in the tenth aspect is made of thermoplastic resincomposition (X10) containing propylene-based polymer (A10) andpropylene-based copolymer (B10) described in detail below, in thefollowing ratio.

Namely, thermoplastic resin composition (X10) is composed ofpropylene-based polymer (A10) in an amount of 0 to 90 parts by weight,preferably 0 to 70 parts by weight, and more preferably 10 to 50 partsby weight, and propylene-based copolymer (B10) in an amount of 10 to 100parts by weight, preferably 30 to 100 parts by weight, and morepreferably 50 to 90 parts by weight. Here, the total of (A10) and (B10)is 100 parts by weight. Thermoplastic resin composition (X10) used forlayer (II-10) may contain components other than (A10) and (B10), forexample, resins other than (A10) and (B10), rubber, inorganic filler,and others as long as the objectives of the tenth aspect of theinvention are not impaired.

With the above range of ratio of (A10) and (B10), the composition isexcellently molded into sheets and also provide solar cell-sealingsheets excellent in heat resistance, transparency, flexibility, and thelike.

With thermoplastic resin composition (X10), desirably, the permanentcompression set measured at 23° C. is 5% to 35% and the permanentcompression set measured at 70° C. is 50% to 70%. With the above rangesof permanent compression sets, the resultant sheet is freed fromdeformation over a wider temperature range from normal temperature tohigh temperature, whereby preventing decrease in power generationefficiency of solar cells. In particular, falling the permanentcompression set measured at 70° C. within the above range is especiallyimportant in order to suppress sheet deformation due to long-termloading such as gravitational load of glass itself in solar cells.

The permanent compression set measured at 23° C. is more preferably 5%to 30%, and still more preferably 5% to 25%. The permanent compressionset measured at 70° C. is more preferably 50% to 68%, and still morepreferably 50% to 66%. The permanent compression set can be measured asfollows in accordance with JIS K6301.

That is, six 2-mm thick press-molded sheets are stacked and compressedby 25%; the stack is kept under this load at a specified temperature(23° C. or 70° C.) for 24 hr; then the compression is released and thethickness of the stack is measured. From the results of the abovemeasurement, the residual strain (permanent compression set) after 24-hrloading is calculated from the following equation.

Residual strain (%)=100×(“thickness before test”−“thickness aftertest”)/(“thickness before test”−“thickness during compressed”)

The Shore A hardness of thermoplastic resin composition (X10) isgenerally 55 to 92, and preferably 60 to 80. Within this range of ShoreA hardness, cracking of solar cells is prevented when the solar cellsare sealed, also the solar cells can attain flexibility, which protectsthe solar cells against deformation and impact shock.

[Propylene-Based Polymer (A10)]

Propylene-based polymers (A10) used in the tenth aspect includehomopolypropylene and copolymers of propylene and at least one C₂-C₂₀α-olefin except propylene. The C₂-C₂₀ α-olefins except propylene includethe same α-olefins as those for isotactic polypropylene (A1) used in thefirst aspect. Also, the preferable range is the same.

These α-olefins may form a random or block copolymer with propylene.

The structural units derived from these α-olefins may be contained in anamount of 35 mol % or less, and preferably 30 mol % or less in thepolypropylene.

Desirably, the melt flow rate (MFR) of propylene-based polymer (A10)measured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238 is 0.01 to 1000 g/10 min and preferably 0.05 to 100 g/10 min.

The melting point of propylene-based polymer (A10) measured with adifferential scanning calorimeter (DSC) is 100° C. or higher, preferably100 to 160° C., and more preferably 110 to 150° C.

Propylene-based polymer (A10) may be either isotactic or syndiotactic,but the isotactic structure is preferred considering heat resistance andothers.

There may be used, if necessary, a plurality kinds of propylene-basedpolymers (A10), for example, two or more components different in meltingpoint or rigidity.

To obtain desired properties, there may be used, as propylene-basedpolymer (A10), one or more polymers selected from homopolypropyleneexcellent in heat resistance (publicly known, generally having 3 mol %or less of copolymerized components except propylene), blockpolypropylene excellent in balance of heat resistance and flexibility(publicly known, generally having 3 to 30 wt % of n-decane-solublerubber components), and random polypropylene excellent in balance offlexibility and transparency (publicly known, generally having a meltingpeak of 100° C. or higher and preferably 110° C. to 150° C. as measuredwith a differential scanning calorimeter (DSC)).

Such propylene-based polymer (A10) can be produced by a similar methodto that for producing isotactic polypropylene (A1) used in the firstaspect.

[Propylene-Based Copolymer (B10)]

Propylene-based copolymer (B10) used in the tenth aspect is a copolymerof propylene and at least one olefin selected from the group consistingof ethylene and C₄-C₂₀ α-olefins. The Shore A hardness of this copolymeris 30 to 80, preferably 35 to 70, and its melting point is lower than100° C. or not observed as measured with a differential scanningcalorimeter (DSC). Here, “melting point is not observed” means that anymelting endothermic peak of crystal having a melting endothermicenthalpy of crystal of 1 J/g or more is not observed in the temperaturerange of −150 to 200° C. The measurement conditions are as described inExamples of the tenth aspect.

In propylene-based copolymer (B10), the α-olefin used as a co-monomer ispreferably ethylene and/or a C₄ to C₂₀ α-olefin.

In propylene-based copolymer (B10), preferably, the content ofpropylene-derived units is 45 to 92 mol % and preferably 56 to 90 mol %,whereas the content of units derived from the α-olefin used as aco-monomer is 8 to 55 mol % and preferably 10 to 44 mol %.

It is desirable that the melt flow rate (MFR) of propylene-basedcopolymer (B10), as measured at 230° C. under a load of 2.16 kg inaccordance with ASTM D1238, is 0.01 to 100 g/10 min and preferably 0.05to 50 g/10 min.

The methods for producing propylene copolymer (B10), although notlimited to, but include a method like that for producing softpropylene-based copolymer (B8) used in the eighth aspect.

It is desirable that propylene-based copolymer (B10) has additionallyindependently the following properties.

Propylene-based copolymer (B10) preferably has the same properties aspropylene/ethylene/α-olefin copolymer (B1) used in the first aspectconcerning triad tacticity (mm-fraction), stress at 100% elongation,crystallinity, glass transition temperature Tg, and molecular weightdistribution (Mw/Mn). These properties provide the same effects.

For instance, the triad tacticity (mm-fraction) of propylene-basedcopolymer (B10) determined by ¹³C-NMR is preferably 85% or more, morepreferably 85% to 97.5%, still more preferably 87% to 97%, andparticularly preferably 90% to 97%. With the above range of triadtacticity (mm-fraction), particularly excellent balance of flexibilityand mechanical strength is attained. This is suitable for the tenthaspect. The mm-fraction can be estimated by the method described in WO2004/087775 from Page 21 line 7 to Page 26 line 6.

For propylene-based copolymer (B10), for instance, the molecular weightdistribution (Mw/Mn, relative to polystyrene standards, Mw:weight-average molecular weight, Mn: number-average molecular weight)measured by GPC is preferably 4.0 or less, more preferably 3.0 or less,and still more preferably 2.5 or less.

When propylene copolymer (B10) has a melting point (Tm in ° C.) in theendothermic curve obtained with a differential scanning calorimeter(DSC), the melting endothermic entalpy AH is generally 30 J/g or less,and the same relation holds between C₃ content (mol %) and meltingendothermic entalpy ΔH (J/g) as that of propylene/ethylene/α-olefincopolymer (B1) used in the first aspect.

Preferred specific examples of propylene-based copolymer (B10) includepropylene/ethylene/α-olefin copolymer (B10-1) below. Use ofpropylene/ethylene/α-olefin copolymer (B10-1) enables to formelectrical/electronic element-sealing sheets excellent in flexibility,heat resistance, mechanical strength, element-sealing performance, andtransparency. Here, “element-sealing performance” means the ability ofreducing the incidence of cracking of elements owing to excellentflexibility when the electrical/electronic elements are embedded.

In propylene/ethylene/α-olefin copolymer (B10-1), the content ofpropylene-derived structural units is 45 to 92 mol %, preferably 56 to90 mol %, and more preferably 61 to 86 mol %; the content ofethylene-derived structural units is 5 to 25 mol %, preferably 5 to 14mol %, and more preferably 8 to 14 mol %; and the content of C₄-C₂₀α-olefin-derived structural units is 3 to 30 mol %, preferably 5 to 30mol %, and more preferably 6 to 25 mol %. The α-olefin is particularlypreferably 1-butene.

Propylene/ethylene/α-olefin copolymer (B10-1) containingpropylene-derived structural units, ethylene-derived structural units,and C₄-C₂₀ α-olefin-derived structural units in the above ratio exhibitsexcellent compatibility with propylene-based polymer (A10) and providessolar cell-sealing sheets with sufficient transparency, flexibility,heat resistance, and scratch resistance.

[Other Components]

Layer (II-10) used in the tenth aspect may optionally contain componentsother than thermoplastic resin composition (X10), as long as theobjectives of the tenth aspect are not impaired.

For instance, the layer may contain, as appropriate, various additivesthat may be added to layer (I-10) (coupling agents including silanecoupling agents, organic peroxides, and/or weathering stabilizers),polyolefins other than the above ethylene-based copolymer, resins and/orrubbers other than polyolefins, and one or more additives selected fromplasticizers, filler, pigments, dyes, antistatic agents, antibacterialagents, fungicides, flame retardants, dispersants, and others.

[Composition and Molding Method of Layer (II-10)]

The thickness of layer (II-10) is generally 0.1 mm to 5 mm, andpreferably 0.1 to 1 mm. With this range of thickness, the layer canprevent damage on glass and solar cells in lamination process and alsoassures sufficient light transmittance, which contributes to generationof high photovoltaic power.

The methods for forming layer (II-10), although not limited to, includeconventional extrusion molding (cast molding, extrusion sheet molding,inflation molding, injection molding, etc.), compression molding,calendar molding, and the like. The above sheet may be embossed.Embossing is preferred since embossed surfaces suppresses mutualblocking of the sheets and functions as cushion for preventing damage onglass and solar cells.

It is desirable that the internal haze of composition for forming layer(II-10) is 0.1% to 15%, and preferably 0.1% to 10% as measured with a0.5-mm thick specimen.

<Electrical/Electronic Element-Sealing Sheet>

The electrical/electronic element-sealing sheets of the tenth aspectinclude any electrical/electronic element-sealing sheet (also called“sheet-shaped sealing material for electrical/electronic elements”)having at least one layer (I-10) made of the above ethylene-basedcopolymer and at least one layer (II-10) made of thermoplastic resincomposition (X10).

Therefore, the number of layer (I-10) may be one, or two or more. Onelayer is preferable from the viewpoint of lowering the cost throughsimplification of sheet configuration, and utilizing light effectivelythrough minimizing the reflection at interface between layers when usedfor sealing an element using light.

The number of layer (II-10) may be one, or two or more. One layer isalso preferable from the same viewpoints as in the case of layer (I-10).

The methods for laminating layer (I-10) and layer (II-10) are notlimited to, but include preferably a method in which layer (I-10) andlayer (II-10) are co-excluded with a conventional melt-extruding machinesuch as cast molding machine, extrusion sheet molding machine, inflationmolding machine, and injection molding machine to prepare a laminate; ora method in which thermoplastic resin composition (X10) is molded toform layer (II-10), on which layer (I-10) is applied in melt orhot-laminated to obtain a laminate.

The electrical/electronic element-sealing sheet of the tenth aspect maycontain a layer other than layer (I-10) and layer (II-10) (also called“additional layer” in the present specification), or may be composed ofonly layer (I-10) and layer (II-10) without such additional layers.

As classification according to objectives, other layers that may beprovided here include a hard coat layer for protecting the front andback surfaces, an adhesive layer, a reflection preventive layer, a gasbarrier layer, an anti-fouling layer, and others. As classificationaccording to material, other layers include a layer made ofultraviolet-curable resin, a layer made of thermoplastic resin, a layermade of polyolefin resin, a layer made of carboxylic acid-modifiedpolyolefin resin, a layer made of fluororesin, and others.

There is no particular limitation on the positional relationship amonglayer (I-10), layer (II-10), and another layer. An appropriate layerconstitution is selected in accordance with the objectives of theinvention. Namely, another layer may be placed between layer (I-10) andlayer (II-10), placed in the outermost layer of theelectrical/electronic element-sealing sheet, or placed in anotherposition.

The number of other layers is not particularly limited, namely, thesheet may contain any number or none of other layers.

From the viewpoint of lowering the cost through simplification of theconstitution, and utilizing light effectively through minimizing thereflection at interfaces between layers when used for sealing an elementusing light, it is particularly preferred to provide only layer (I-10)and layer (II-10), each one layer, directly bonded together withoutother layer.

The electrical/electronic element-sealing sheet related to the tenthaspect is produced by laminating a plurality of layers. The method forlamination is not particularly limited. The laminate can be produced,for example, dry lamination using an appropriate adhesive, for example,a maleic anhydride-modified polyolefin resin (“Admer” (TM, availablefrom Mitsui Chemicals, Inc.), “Modic” (TM, available from MitsubishiChemical Corp.), etc.), a low- (or non-)crystalline soft polymer such asunsaturated polyolefin, an acrylic adhesive such asethylene/acrylate/maleic anhydride ternary copolymer (for example,“Bondine” (TM, available from Sumika CDF Chemical Co., Ltd.)),ethylene/vinyl acetate copolymer, or an adhesive resin compositioncontaining these adhesives; or by heat lamination. An adhesive havingheat resistance of about 120° C. to 150° C. is preferably used, and apolyester or polyurethane adhesive is suitable. To improve the adhesionof both layers, for example, these layers may be treated with a silanecoupling agent or titanium coupling agent, or may be exposed to corona,plasma, and others.

For the electrical/electronic element-sealing sheet of the tenth aspect,the internal haze is preferably 0.1% to 15%, and more preferably 0.1% to10%. Note that, in this case, the internal haze is measured with thesealing sheet irrespective of its thickness.

The light transmittance is preferably 86% or more, and more preferably88% or more. The sheet having the above light transmittance less lowersthe power generation efficiency, and is suitably used for the tenthaspect.

[Solar Cell-Sealing Sheet]

The electrical/electronic element-sealing sheet of the tenth aspect isexcellent in heat resistance, transparency, and flexibility, so that thesheet is suitable for use as a sealing sheet for electrical/electronicelements using intense light illumination, in particular, a sealingsheet for solar cells (a solar cell-sealing sheet or a sheet-shapedsealing material for solar cells). In using as a solar cell-sealingsheet, the above electrical/electronic element-sealing sheet may be usedas it is or may be used after processing such as addition of anotherlayer.

[Solar Cell Module]

A solar cell module generally has a structure in which a solar cellelement made of polycrystalline silicon or the like is sandwichedbetween solar cell-sealing sheets to form a laminate and both front andback surfaces of the laminate are further covered with protectivesheets. Namely, a typical structure of solar cell module is representedas solar cell module-protecting sheet (front protective sheet)/solarcell-sealing sheet/solar cell element/solar cell-sealing sheet/solarcell module-protecting sheet (back protective sheet). However, the solarcell module, which is one of preferred embodiments of the tenth aspect,is not limited to the above structure but may have any convenient layerother than the above as long as the objectives of the tenth aspect arenot impaired. Specifically, the module may have, typically, although notlimited to, an adhesive layer, an impact-absorbing layer, a coatinglayer, an reflection preventive layer, a back re-reflection layer, alight diffusive layer, and the like. These layers may be formed in anyposition suitable for objectives and characteristics thereof withoutparticular limitation.

[Front Protective Sheet for Solar Cell Module]

Although there is no particular limitation on the front protective sheetfor solar cell modules, but it is preferably possesses weatherresistance, water repellency, anti-fouling property, mechanicalstrength, and other performances for assuring long-term reliability ofsolar cell modules exposed to outdoor environment, because the sheet ispositioned in the outmost layer of the solar cell module. In addition,the sheet preferably has high transparency and low optical loss in orderto utilize sun light efficiently.

The materials for the front protective sheet for solar cell modulesinclude a resin film made of polyester resin, fluororesin, acrylicresin, or the like and a glass plate.

Polyester resin, particularly polyethylene terephthalate resin issuitably used for the resin film since it has superiority intransparency, mechanical strength, cost, and others.

Fluororesins with excellent weather resistance are also suitably used.Specifically, there may be mentioned, tetrafluoroethylene/ethylenecopolymer (ETFE), polyvinyl fluoride resin (PVF), polyvinylidenefluoride resin (PVDF), poly(tetrafluoro)ethylene resin (TFE),tetrafluoroethylene/hexafluoropropylene copolymer (FEP), andpoly(trifluorochloro)ethylene resin (CTFE). In weather resistance,polyvinylidene fluoride resin is superior whereastetrafluoroethylene/ethylene copolymer is excellent in both weatherresistance and mechanical strength. It is desirable to treat the filmsurface treated with corona or plasma to improve adhesion to the abovesealing resin. An oriented film may also be used for improvingmechanical strength.

When the glass plate is used as the front protective sheet for solarcell modules, the total light transmittance of glass plate is preferably80% or more, and more preferably 90% or more in the wavelength of 350 to1400 nm. As the above glass plate, a white glass plate with lowabsorption in the infra red region is usually used, but even a blueglass plate has a minor effect on output characteristics of solar cellmodules if its thickness is 3 mm or less. There is available reinforcedglass, which is heat-treated for enhancing the mechanical strength ofthe glass plate, but a float glass without heat treatment may be alsoused. The light receiving face of the glass plate may have reflectionpreventive coating to suppress reflection.

As described above, the polyester resin and the glass have excellentproperties as the front protective sheet, but they are known to berelatively difficult to be bonded. Layer (I-10) in the solarcell-sealing sheet related to the tenth aspect is made of a specificpolyethylene copolymer with excellent adhesion and preferably contains asilane coupling agent, so that layer (I-10) has excellent adhesion tothe polyester resin and the glass. Therefore, in the solar cell moduleof the tenth aspect, it is desirable to bond the solar cell-sealingsheet to the front protective sheet through layer (I-10).

[Back Protective Sheet for Solar Cell Modules]

There is no particular limitation on the back protective sheet for solarcell modules, but the sheet is required to have similar propertiesincluding weather resistance and mechanical strength to those of thefront protective sheet, since the sheet is positioned in the outmostlayer of the solar cell module. Accordingly, the back protective sheetfor solar cell modules may be made of a similar material to that of thefront protective sheet. Namely, the polyester resin and the glass arepreferably used.

Layer (I-10) of the solar cell-sealing sheet related to the tenth aspectis made of the specific polyethylene copolymer with excellent adhesionand preferably contains the silane coupling agent, so that layer (I-10)has excellent adhesion to the polyester resin and the glass. Therefore,in the solar cell module of the tenth aspect, it is desirable to bondthe solar cell-sealing sheet to the back protective sheet through layer(1-10).

The back protective sheet is not essentially required to transmit sunlight, so that the transparency, which is required for the frontprotective sheet, is not always requested. Therefore, a reinforcingplate may be attached to the sheet in order to increase the mechanicalstrength of the solar cell module or to prevent distortion and straincaused by temperature change. For instance, a steel plate, a plasticboard, and an FRP (glass-reinforced plastic) board are preferably used.

[Solar Cell Element]

As the solar cell element of the tenth aspect of the present invention,any element that can generate electricity based on the photovoltaiceffect of semiconductors, for instance, solar cells of silicon (singlecrystal, polycrystalline, and non-crystalline (amorphous) silicon),solar cells of compound semiconductor (Group III/V, Group II/VI, etc.),wet solar cells, organic semiconductor solar cells, and others. Amongthese, polycrystalline silicon solar cells are preferable in terms ofcost performance and others.

Both silicon and compound semiconductors are known to exhibit excellentproperties as solar cell elements, but they are also known to be liableto damage by external stress, impact, or the like. Layer (II-10) in thesolar cell-sealing sheet of the tenth aspect is made of specificthermoplastic resin composition (X10) with excellent flexibility, sothat layer (II-10) absorbs the stress and impact loaded on the solarcell elements and effectively prevents damage on the solar cellelements. Therefore, in the above solar cell module, it is desirable tobond the solar cell-sealing sheet of the tenth aspect to the solar cellelement through layer (II-10).

Since layer (II-10) is made of thermoplastic resin composition (X10),the solar cell element can be relatively easily removed from the solarcell module even after the module is once fabricated. Such excellentrecyclability is also preferable.

[Electric Power Generator]

The solar cell module, which is a preferred embodiment of the tenthaspect, is excellent in productivity, power generation efficiency,service life, and others. Therefore, an electric power generator usingthe solar cell module is also excellent in cost performance, powergeneration efficiency, service life, and others, and practicallyvaluable.

The above electric power generator is suitable for long-term uses,regardless indoor or outdoor, including uses as a power unit on theroofs of houses, a portable power source for camping and other outdoorapplications, an auxiliary power unit for car batteries, and others.

EXAMPLES

Hereinafter, the present invention will be explained in detail withreference to Examples, but the present invention is not limited to theseexamples.

<First Aspect of Invention>

The followings are explanation on (i) preparation method and propertiesof starting materials, (ii) preparation of specimens, and (iii) testmethods used for evaluation in Examples and Comparative Examples.

(i) Preparation method and properties of starting materials (a)Synthesis of propylene/ethylene/butene random copolymer (PEBR)

In a 2000-mL polymerization reactor fully purged with nitrogen, 833 mLof dry hexane, 100 g of 1-butene, and 1.0 mmol of triisobutylaluminumwere charged at normal temperature, the temperature in the reactor iselevated to 40° C., and propylene was supplied so that the pressure inthe reactor increased to 0.76 MPa, and then ethylene was supplied toadjust the pressure at 0.8 MPa. To the reactor was added a toluenesolution in which 0.001 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.3 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corporation) had beencontacted, and the polymerization was conducted for 20 min while theinside temperature was kept at 40° C. and the inside pressure was keptat 0.8 MPa by supplying ethylene. Then, 20 mL of methanol was added toterminate polymerization. After the pressure was released, the polymerwas precipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 36.4 g of PEBR. Forthis polymer, intrinsic viscosity [n] was 1.81 dl/g, glass transitiontemperature Tg was −29° C., ethylene content was 17 mol %, butenecontent was 7 mol %, molecular weight distribution (Mw/Mn) was 2.1, andmm-fraction was 90%. No distinctive melting peak was observed (ΔH wasless than 0.5 J/g) with a DSC. The basic properties of the present PEBRare shown in Table 1-1.

(b) Properties of Other Starting Materials

Table 1-1 shows the basic properties of other starting materials usedfor the present evaluation, which are homopolypropylene (hPP), randompolypropylene (rPP), ethylene/butene random copolymer (EBR),styrene/ethylene butene/styrene copolymer (SEBS), and low-densitypolyethylene (LDPE). In the present evaluation, as a softener was used aparaffin oil, “PW-90” available from Idemitsu Kosan Co., Ltd. (kinematicviscosity at 40° C.: 95.5 cst).

TABLE 1-1 Properties of Starting Materials hPP rPP LDPE PEBR EBR-1 SEBSMelting point ° C. 163 140 110 not not Tuftec observed observed H1221MFR(230° C.) g/10 min  7 7    6.5 8.5 2.6 Density kg/m³ 920 861C2(ethylene) mol % 2.2  99< 17 81 content C3(propylene) mol %  99< 96.376 content C4(butene) mol % 1.5 7 19 content * SEBS: “Tuftec H1221” (TM)available from Asahi Kasei Chemicals Corp.

For both hPP and rPP in the table, the isotactic pentad fraction(mmmm-fraction) was 0.95 or more.

1. Melting Point and Glass Transition Temperature

In exothermic/endothermic curve measured with a DSC, the temperature atwhich the maximum melting peak appeared in heating was counted as Tm,and the secondary transition point observed in the endothermic curvebetween −100° C. and 0° C. was counted as Tg. A sample loaded on analuminum pan was heated to 200° C. at 100° C./min, kept at 200° C. for 5min, cooled to −150° C. at 10° C./min, and heated at 10° C./min duringwhich the exothermic/endothermic curve was recorded.

2. Density

A strand that had been used for MFR measurement at 190° C. under a loadof 2.16 kg was kept at 120° C. for 1 hr, gradually cooled to roomtemperature over 1 hr, and used for density measurement with a densitygradient column.

3. MFR

MFR at 230° C. under a load of 2.16 kg was measured in accordance withASTM D1238.

4. Co-Monomer (C2, C3, and C4) Contents

The contents were determined by ¹³C-NMR spectrum.

5. Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(ii) Preparation Methods of Specimens

Starting materials were kneaded in the ratios described in Table 1-2with a Labo plast-mill (available from Toyo Seiki Seisaku-sho, Ltd.) andmolded into a 2-mm thick sheet with a press molding machine (heating:190° C. for 7 min, cooling: 15° C. for 4 min, cooling speed: about −40°C./min).

(iii) Evaluation Items for Properties

1. Permanent Compression Set

Six 2-mm thick press-molded sheets were stacked, compressed by 25%, keptunder load for 24 hr at 23° C., 50° C., or 70° C., and the residualstrain (given by the following equation) was examined.

Residual strain=100×“strain after test” (“thickness beforetest”−“thickness after test”)/“strain” (“thickness beforetest”−“thickness on compression”)

2. Mechanical Properties

In accordance with JIS K7113-2, yield stress (YS), tensile strength atbreak (TS), elongation at break (chuck-to-chuck distance, EL), andYoung's modulus (YM) were measured using a 2-mm thick press-moldedsheet.

3. Hardness

In accordance with ASTM D2240, using two 2-mm thick press-molded sheetsstacked, Shore-A hardness was evaluated.

4. Oil-Acceptance

After a molded specimen was kept in an oven at 70° C. for 14 days,oil-bleeding in the surface was evaluated by visual observation.

Examples 1-1 to 1-8, Comparative Examples 1-1 to 1-5, and ReferenceExample 1-1

For sheet specimens with the composition described in Tables 1-2 and1-3, the mechanical properties, hardness, and permanent compression setcharacteristics are shown in Tables 1-2 and 1-3. The results of oilacceptance evaluation are shown in Table 1-4.

TABLE 1-2 Examples Example Example Example Example Example ExampleExample Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 (A1) hPP (pbw) 20 40 4040 (A1) rPP (pbw) 50 50 50 50 (B1) PEBR (pbw) 70 50 50 25 25 40 25 25(C1) SEBS (pbw) 10 10 10 25 25 10 15 15 (D1) EBR (pbw) 10 10 10 (E1)PW-90 (pbw) 20 10 10 YS MPa none 7.7 none none none none none none TSMPa  15< 21 16  22<  17< 18  17<  12< EL % 800< 580 520  800< 800< 460800< 800< YM MPa 23 118 75 74 45 123  80 50 Shore A 80 95 92 88 83 97 9286 CS 23° C. 31 40 37 34 35 31 33 36 50° C. 56 55 57 54 56 57 55 58 70°C. 65 60 65 69 71 70 71 67 Note: pbw = parts by weight

TABLE 1-3 Comparative Examples and Reference Example ComparativeComparative Comparative Comparative Comparative Reference Example 1-1Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-1 (A1) hPP(pbw) 20 40 40 40 40 LDPE (pbw) 40 (B1) PEBR (pbw) 60 (C1) SEBS (pbw) 6060 (D1) EBR (pbw) 80 60 60 (E1) PW-90 (pbw) 20 40 20 YS MPa none nonenone none none none TS MPa 2.2 6.6 21 11 13 17 EL % 480 70 440 340  790 550  YM MPa 10 182 129 91 39 77 Shore A 66 90 93 88 85 92 CS 23° C. 3634 23 27 26 36 50° C. 99 93 62 63 61 52 70° C. 100 95 88 91 77 62 Note:pbw = parts by weight

TABLE 1-4 Oil-acceptance (Examples, Comparative Examples, and Referenceexample) Comparative Reference Example Example Example 1-3 1-3 1-1 (A1)hPP 40 40 40 (B1) PEBR 50 60 (C1) SEBS 10 60 (E1) PW-90 20 20 20 CS 70°C. 65 88 62 Oil-acceptance Excellent Excellent Poor Excellent: nooil-bleeding, Poor: oil-bleeding observed

<Second Aspect of Invention>

(i) The properties of starting materials used in the present Examplesand Comparative Examples are described below.

(1) Propylene/α-Olefin Random Copolymer (PBR)

Propylene/1-butene copolymer (Butene content=27 mol %, Tm=73° C.,MFR(230° C.)=7 g/10 min, Mw/Mn=2.1) was used. The mm-Fraction was 91%.The copolymer was produced with a metallocene catalyst described in WO2004/087775.

(2) Styrene-Based Elastomer (SEBS)

SEBS “Tuftec H1062”™ available from Asahi Kasei Chemicals Corp. wasused.

(3) Isotactic Polypropylene (rPP)

Propylene/ethylene/1-butene random copolymer (Tm=140° C., MFR(230° C.)=7g/10 min, mmmm-Fraction=0.96, Mw/Mn=4.8) was used.

(4) Ethylene/α-Olefin Copolymer (EBR)

Ethylene/1-butene copolymer (density=870 kg/m³, Tm=53° C., MFR(230°C.)=7 g/10 min, Mw/Mn=2.1) was used.

(5) Softener (Oil)

Paraffin oil “PW-90”™ available from Idemitsu Kosan Co., Ltd. (Kinematicviscosity at 40° C.: 95.5 cSt) was used.

The above properties were measured by the following methods.

(1) Melting Point

In an exothermic/endothermic curve measured with a DSC, the temperatureat which the maximum melting peak appeared in heating was counted as Tm.Here, the sample loaded on an aluminum pan was heated to 200° C. at 100°C./min, kept at 200° C. for 5 min, cooled to −150° C. at 10° C./min, andheated at 10° C./min during which the exothermic/endothermic curve wasrecorded.

(2) Co-Monomer (C2, C3, and C4) Contents

The contents were determined by ¹³C-NMR spectrum.

(3) MFR

MFR at 230° C. under a load of 2.16 kg was measured in accordance withASTM D1238.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Density

The density was measured in accordance with ASTM D1505.

(ii-1) Preparation of Samples

Starting materials were kneaded in the ratio described in Tables 2-1 and2-2 with a Labo plast-mill (available from Toyo Seiki Seisaku-sho, Ltd.)and molded into a 2-mm thick sheet with a press molding machine(heating: 190° C. for 7 min, cooling: 15° C. for 4 min, cooling speed:about −40° C./min).

(iii-1) Evaluation Methods and Items

(1) Flexibility (YM)

Young's modulus (YM) was measured with a 2-mm thick press-molded sheetin accordance with JIS K7113-2.

(2) Abrasion Resistance (ΔGloss)

Each sample was abraded using a “Gakushin” abrasion testing machineavailable from Toyo Seiki Seisaku-sho Ltd. equipped with a 45R SUS-madeabrasion indenter weighing 470 g whose tip was covered with cotton clothNo. 10, under conditions of 23° C., the number of reciprocations of 100times, a reciprocation speed of 33 times/min, and a stroke of 100 mm.The gloss retention percentage with abrasion, AGloss, was calculated asfollows.

Gloss retention percentage=Gloss after abrasion/Gloss beforeabrasion×100.

The larger ΔGloss is, the better the abrasion resistance is.

(3) Whitening Resistance

A specimen was folded by 180° to form a symmetric shape. After acylindrical weight with 5 cm of radius and 10 kg of weight was loaded onthe folded specimen for 1 hr, the whitening level was evaluated byvisual observation.

Excellent: no whitening, Do: slight whitening, Poor: marked whitening.

(4) Low-Temperature Kneadability

With a Labo plast-mill, a composition was kneaded (40 rpm, 5 min) at 150to 160° C. and the kneadability was evaluated. Excellent: kneadable,Poor: not kneadable (Non-melted part is present), NE: not evaluated.

Examples 2-1 to 2-5

Using samples prepared in (ii-1) at the blending proportions describedin Table 2-1, items (1) to (3) above were evaluated. The results arealso shown in Table 2-1.

Comparative Examples 2-1 and 2-2

Using samples prepared in (ii-1) at the blending proportions describedin Table 2-2, items (1) to (3) above were evaluated. The results arealso shown in Table 2-2. Item (4) was evaluated for only Example 2-4 andComparative Example 2-1.

TABLE 2-1 Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple 2-1 2-2 2-32-4 2-5 (B2) PBR (pbw) 70 50 50 50 70 (C2) SEBS (pbw) 30 30 20 30 30(A2) rPP (pbw) 20 20 (D2) EBR (pbw) 10 20 (E2) Oil (pbw) 30 YM MPa 160250 265 105 85 ΔGloss % 65 83 76 52 54 Whitening Excel- Excel- Excel- DoExcel- resistance lent lent lent lent Low-temperature NE NE NE Excel- NEkneadability lent Note: pbw = parts by weight

TABLE 2-2 Comparative Comparative Example Example 2-1 2-2 (A2) rPP (pbw)50 40 (D2) EBR (pbw) 50 60 YM MPa 180  110  ΔGloss % 35 20 WhiteningPoor Poor resistance Low-temperature Poor NE kneadability Note: pbw =parts by weight

The above evaluation shows that the molded articles formed fromthermoplastic resin composition (X2) related to the second aspect ofinvention are superior to those made of conventional compositionscomposed of polypropylene and ethylene/α-olefin copolymer in balance offlexibility and scratch and whitening resistances. In addition,thermoplastic resin composition (X2) is kneadable at low temperature, sothat thermoplastic resin composition (X2) can be processed under widermolding conditions including dynamic crosslinking.

(ii-2) Preparation of Samples

The starting materials described in Table 2-3 were kneaded with a 40-mmΦextruder to make pellets, which were melt-processed with an injectionmolding machine under the following conditions to prepare samples.

Preset temperatures: H3/H2/H1/NH=180/200/210/210° C.

Mold temperature: 40° C.

Injection pressure: 1000/800 kgf/cm² (square plate), 400/280 kgf/cm²(specimen)

Mold cycle: primary/secondary/cooling=10/10/30 sec

(iii-2) Evaluation Methods and Items

(1) Tensile Strength at Break, Elongation at Break, and Modulus inTension (Young's Modulus)

The tensile strength at break, elongation at break, and modulus intension were measured in accordance with ASTM D638 using ASTM-IVinjection-molded specimens at 23° C. and a tensile speed of 50 mm/min.

(2) Total Haze

The total haze was measured with an injection-molded square plate,110×110×3 (thickness) mm in size.

(3) Falling Ball Whitening Test

A steel ball weighing 287 g was dropped from a height of 80 cm on aninjection-molded square plate (110×110×3 (thickness) mm) held on acylindrical jig with an inside diameter of 55 mm. The change in hue L(L-value in specular component excluded method) was evaluated inwhitened part where the steel ball was directly hit. The smaller ΔL is,the more excellent whitening resistance is.

ΔL=L(after test)−L(before test)

(4) Impact Resistance

Izod impact strength was measured in accordance with ASTM D785.

Measurement temperature: 0° C., Specimen size: 12.7 (width)×64(length)×3.2 (thickness) mm

(5) Anti-Blocking Property

Two injection-molded square plates were stacked and fixed together witha tape, and the stack was loaded with 5 kg of weight at room temperaturefor 1 week. Stickiness experienced when the plates were separated fromeach other was evaluated.

Excellent: no stickiness, Do: slight stickiness, Poor: marked stickiness

Example 2-6, Comparative Examples 2-3 to 2-5, and Reference Examples 2-1and 2-2

Using samples prepared in (ii-2), items (1) to (5) above were evaluated.The results are shown in Table 2-3.

TABLE 2-3 Example Comparative Reference Comparative ComparativeReference 2-6 Example 2-3 example 2-1 Example 2-4 Example 2-5 example2-2 (B2) PBR (pbw) 7.5 15 7.5 (C2) SEBS (pbw) 7.5 15 (A2) rPP (pbw) 85100 85 85 85 85 (D2) EBR (pbw) 15 7.5 Tensile MPa 38 41 40 37 32 36strength at break Elongation % 540 500 570 520 420 490 at break Modulusin MPa 730 950 790 660 680 740 tension Total haze % 62 72 64 63 78 74Impact J/m 170 20 35 360 210 85 resistance (0° C.) Surface ExcellentExcellent Excellent Poor Do Excellent stickiness Hue L 29.0 28.5 28.029.0 31.0 29.0 After L 29.5 30.0 29.5 30.5 35.0 32.0 ball drop ΔL 0.51.5 0.5 1.5 4.0 3.0 Note: pbw = parts by weight

As clearly seen in Table 2-3, the composition related to the secondaspect of invention (Example 2-6) is particularly excellent in balanceof tensile elasticity, transparency, impact resistance, and whiteningresistance.

<Third Aspect of Invention> (1) Measurement of Intensity ofMagnetization in Decay Process Due to Transverse Relaxation Up to 1000μs in Pulse NMR Solid-Echo Experiment Observed for ¹H

The starting materials used in the present examples are as follows:

(A3-1) Isotactic Polypropylene (rPP)

Propylene/ethylene/1-butene random copolymer (Mw/Mn=4.8, MFR(230° C.)=7g/10 min, Tm=140° C., mm-Fraction=97%, Content of n-decane-insolublecomponents=98 wt %, Tm of n-decane-insoluble components=140° C.,Propylene content in n-decane-insoluble components=98 mol %, Intrinsicviscosity [η] of n-decane-insoluble components=1.9 dl/g) was used.

(B3) Propylene/Ethylene/1-Butene Copolymer (PEBR)

Ethylene content=14.0 mol %, 1-Butene content=19 mol %, MFR=7 g/10 min,Intrinsic viscosity [η]=2.0 dl/g, Melting point=not observed (ΔH: lessthan 0.5 J/g), Molecular weight distribution (Mw/Mn)=2.0, Shore Ahardness=45, mm-Fraction=92% (PEBR was prepared by the method describedin WO 2004/87775.)

Specifically, PEBR was prepared as follows. In a 2000-mL polymerizationreactor fully purged with nitrogen, 917 mL of dry hexane, 85 g of1-butene, and 1.0 mmol of triisobutylaluminum were charged at normaltemperature, the inside temperature of the reactor was elevated to 65°C., propylene was introduced so that the inside pressure of the reactorincreased to 0.77 MPa, and then ethylene was supplied so as to adjustthe inside pressure to 0.78 MPa. Into the reactor was added a toluenesolution in which 0.002 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corp.) had beencontacted, and polymerization was conducted for 20 min while the insidetemperature was kept at 65° C. and the inside pressure was kept at 0.78MPa by adding ethylene. The polymerization was terminated by adding 20mL of methanol, the pressure was released, and the polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 60.4 g of the desiredcopolymer.

(b3-1) Soft Propylene-Based Copolymer (PER)

“VISTAMAXX VM1100”™ available from Exxon Mobil Corp. (Tm=159° C.,Ethylene content=20 mol %, mm-Fraction=93%, Shore A hardness=66) wasused.

(b3-2) Non-Crystalline PP

There was used a composition (Shore A hardness of the composition=61)obtained by melt-kneading 85 wt % of non-crystalline propylene/1-butenecopolymer (Melting point=not observed, 1-Butene content=3 mol %,mm-Fraction=11%, MFR=3 g/10 min) and 15 wt % of isotactichomopolypropylene (Tm=160° C.)

(C3) Styrene/Ethylene Butylene/Styrene Copolymer (SEBS)

“Tuftec H1062”™ available from Asahi Kasei Chemicals Corp. (Tm=notobserved, Shore A hardness=67) was used.

(D3) Ethylene/1-butene copolymer (EBR)

Density=870 kg/m³, Melting point=53° C., MFR(230° C.)=7.2 g/10 min,Mw/Mn=2.1, Shore A hardness=71

The properties of the above starting materials were measured by thefollowing methods:

(1) Melting Point (Tm)

In an exothermic/endothermic curve measured with a DSC, the temperatureat which the maximum melting peak appeared in heating was regarded asTm. Here, the sample loaded on an aluminum pan was heated to 200° C. at100° C./min, kept at 200° C. for 5 min, cooled to −150° C. at 20°C./min, and heated at 20° C./min during which the exothermic/endothermiccurve was recorded.

(2) Co-monomer (C2, C3, and C4) contents and mm-Fraction

The contents and mm-fraction were determined by ¹³C-NMR spectrum.

(3) MFR

MFR at 230° C. under a load of 2.16 kg was measured in accordance withASTM D1238.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Shore a Hardness

The Shore A hardness was measured in accordance with JIS K6301.

(6) Density

The density was measured in accordance with ASTM D1505.

(7) Content of n-Decane-Insoluble Components

n-Decane extraction test was conducted by the method described in thepresent specification, and the content of n-decane-insoluble componentswas obtained from the following equation:

Content of n-decane insoluble components (wt %)=100−content ofn-decane-soluble components (wt %).

Example 3-1

A polymer composition containing 80 wt % of rPP (A3-1) and 20 wt % ofPEBR (B3) was obtained by kneading with a Labo plast-mill available fromToyo Seiki Seisaku-sho, Ltd. at 190° C. for 5 min (40 rpm, chargedstarting materials occupied 75% of mill volume). Namely, the polymercomposition contained 78.4 wt % of n-decane-insoluble propylene-basedpolymer (A3) and 20 wt % of PEBR (B3); in other words, (A3) was 79.7 wt%, and (B3) was 20.3 wt % relative to 100 wt % of the total of (A3) and(B3); hence f_(B) was 0.203.

The composition thus obtained was molded into a 2-mm thick sheet with apress molding machine (heating: 190° C. for 17 min, cooling: 15° C. for4 min, cooling speed: about −40° C./min). A sample was cut out of thissheet and used for the pulse NMR measurement (solid-echo experimentobserved for ¹H at 100° C.) by the method described in the presentspecification. FIG. 3-1 shows the intensity of magnetization in decayprocess M(t)_(C1) (corresponding to M(t)_(X-1)) in transverse relaxationprocess up to 1000 μs.

FIG. 3-1 also shows the calculated intensity of magnetization in decayprocess, M(t)_(CAL1), which was calculated from intensities ofmagnetizations in decay processes of rPP(A3-1) alone and PEBR(B3) alone,using equation 3-1-2 in the present specification, considering that thecontent of n-decane-insoluble components in rPP(A3-1) was 98 wt % andf_(B) was 0.203. The differences, M(t)_(CAL)−M(t)_(C), at observationtime, t, of 500 and 1000 μs (ΔM(500) and ΔM(1000), respectively) areshown in Table 3-1. (In Example 3-2 and Comparative Examples 3-1 to 3-3below, the results were analyzed similarly to above.)

Example 3-2

Intensity of magnetization in decay process M(t)_(C2) was measured bythe same method as that in Example 3-1 except that 50 wt % of rPP (A3-1)and 50 wt % of PEBR (B3) were used (namely, n-decane-insolublepropylene-based polymer (A3) was 49 wt % and PEBR (B3) was 50 wt %;based on 100 wt % of the total of (A3) and (B3), (A3) was 49.5 wt %,(B3) was 50.5 wt %, and hence f_(B) was 0.505). The results are shown inFIG. 3-2. FIG. 3-2 also shows the calculated intensity of magnetizationin decay process M(t)_(CAL2) obtained from the intensities ofmagnetizations in decay processes measured for rPP (A3-1) alone andPEBR(B3) alone using equation 3-1-2 in the present specification,considering that the content of n-decane-insoluble components inrPP(A3-1) was 98 wt % and f_(B) was 0.505.

Comparative Example 3-1

Intensity of magnetization in decay process M(t)_(C3) was measured bythe same method as that in Example 3-1 except that 50 wt % of rPP(A3-1)and 50 wt % of PER (b3-1) were used. The results are shown in FIG. 3-3.FIG. 3-3 also shows the calculated intensity of magnetization in decayprocess M(t)_(CAL3) obtained from the intensities of magnetizations indecay processes measured for for rPP (A3-1) alone and PER (b3-1) aloneusing equation 3-1-2 in the present specification, considering that thecontent of n-decane-insoluble components in rPP(A3-1) was 98 wt % andf_(B) was 0.505.

Comparative Example 3-2

Intensity of magnetization in decay process M(t)_(C5) was measured bythe same method as that in Example 3-1 except that 50 wt % of rPP(A3-1)and 50 wt % of SEBS (C3) were used. The results are shown in FIG. 3-4.FIG. 3-4 also shows the calculated intensity of magnetization in decayprocess M (t)_(CAL5) obtained from the intensities of magnetizations indecay processes measured for rPP(A3-1) alone and SEBS(C3) alone usingequation 3-1-2 in the present specification, considering that thecontent of n-decane-insoluble components in rPP(A3-1) was 98 wt % andf_(B) was 0.505.

Comparative Example 3-3

Intensity of magnetization in decay process M(t)_(C6) was measured bythe same method as that in Example 3-1 except that 50 wt % of rPP(A3-1)and 50 wt % of EBR (D3) were used. The results are shown in FIG. 3-5.FIG. 3-5 also shows the calculated intensity of magnetization in decayprocess M (t)_(CAL6) obtained from the intensities of magnetizations indecay processes measured for rPP(A3-1) alone and EBR(D3) alone usingequation 3-1-2 in the present specification, considering that thecontent of n-decane-insoluble components in rPP(A3-1) was 98 wt % andf_(B) was 0.505.

TABLE 3-1 Exam- Comparative Comparative Comparative ple Example ExampleExample Example 3-1 3-2 3-1 3-2 3-3 ΔM 0.05 0.06 0.01 0.00 0.00  (500)ΔM 0.10 0.09 0.00 0.00 0.00 (1000)

The compositions using PBER (B3) related to the third aspect of thepresent invention satisfy equation 3-1 in the entire range ofobservation time t from 500 to 1000 μs.

(2) Evaluations for Mechanical Properties, Scratch Resistance, andTransparency Examples 3-11 and 3-12, and Comparative Examples 3-11 to3-16

Each of rPP(A3-1) alone, which served as a reference, and the polymercompositions with the component ratios described in Table 3-2 wasmelt-kneaded and press-molded into a 2-mm thick sheet. With this sample,the mechanical properties, scratch resistance, transparency, and thermalwhitening resistance were evaluated.

Evaluation Methods: (i) Mechanical Properties

Yield stress (YS), elongation at yield [EL(YS)], tensile strength atbreak (TS), elongation at break [EL(TS)], and Young's modulus (YM) weremeasured with a 2-mm thick press-molded sheet in accordance with JISK7113-2.

(ii) Scratch Resistance (Gloss Retention Percentage)

Each sample was abraded using a “Gakushin” abrasion testing machineavailable from Toyo Seiki Seisaku-sho Ltd. equipped with a 45R SUS-madeabrasion indenter weighing 470 g whose tip was covered with cotton clothNo. 10, under conditions of 23° C., the number of reciprocations of 100times, a reciprocation speed of 33 times/min, and a stroke of 100 mm.The gloss retention percentage with abrasion was calculated as follows:

Gloss retention percentage=Gloss after abrasion/Gloss beforeabrasion×100.

(iii) Transparency (Internal Haze)

Measurement was performed with a digital haze/tubidimeter “NDH-20D”available from Nippon Denshoku Kogyo Co., Ltd. for a 2-mm thickpress-molded sheet immersed in cyclohexanol. Internal haze wascalculated from the following equation:

Internal haze (%)=100×(Diffuse transmission)/(Total transmission).

(iv) Whitening Resistance (Thermal Whitening Resistance)

After each press-molded sheet was heated in a hot-air drier at 120° C.for 3 min and at 160° C. for 3 min, whitening resistance was evaluatedby visual observation.

A: no whitening, B: slight whitening, C: marked whitening.

TABLE 3-2 Example Example Comparative Comparative rPP (A3) 3-11 3-12Example 3-11 Example 3-12 Elastomers alone PBER(B3) PER(b3-l) *1 0.0 0.20.5 0.2 0.5 Yield stress YS MPa 27.0 18.7 8.5 18.0 10.5 Elongation atyield point EL(YS) % 7.2 11.0 20.5 8.8 11.0 Tensile strength at break TSMPa 34.0 29.5 25.0 24.0 24.9 Elongation at break EL(TS) % 450 530 590460 550 Young's modulus (YM) MPa 610 150 680 290 Scratch resistance % 9796 82 78 33 (Gloss retention) Transparency % 81 75 49 86 91 Whiteningresistance B A A C C (Thermal whitening resistance) ComparativeComparative Comparative Comparative Example 3-13 Example 3-14 Example3-15 Example 3-16 Elastomers Non-crystalline PP(b3-2) SEBS(C3) EBR(D3)*1 0.2 0.5 0.2 0.2 Yield stress YS MPa 16.2 10.4 18.2 18.2 Elongation atyield point EL(YS) % 11.5 17.4 7.5 8.0 Tensile strength at break TS MPa21.8 17.5 29.0 21.8 Elongation at break EL(TS) % 440 520 720 440 Young'smodulus (YM) MPa 540 210 770 720 Scratch resistance % 93 88 80 62 (Glossretention) Transparency % 73 45 82 89 Whitening resistance C C C C(Thermal whitening resistance) *1: Fraction of elastomer (B3), (b3-1),(b3-2), (C3), or (D3) blended

The propylene-based polymer compositions using PEBR (B3) related to thethird aspect of invention, which satisfy formulae 3-2 and 3-3 in thepresent specification, are superior to other soft polypropylenematerials (b3-1) and (b3-2) and conventional elastomers (C3) and (D3) inflexibility, transparency, mechanical properties, scratch resistance,and whitening resistance (thermal whitening resistance).

(3) Molded Sheets and Wrap Films (3-1) Evaluation of WhiteningResistance for Molded Sheets Examples 3-21 to 3-26 and ComparativeExamples 3-21 to 3-30

Each of PEBR (B3), PER (b3-1), non-crystalline PP (b3-2), SEBS (C3), EBR(D3), rPP (A3-1), and isotactic block polypropylene (bPP) (A3-2) belowwas molded into a 500-μm thick sheet, with which whitening resistancewas evaluated (Tables 3-3-1, 3-3-2).

(A3-2) Isotactic Block Polypropylene (bPP)

Tm=158° C., MFR(230° C.)=1.3 g/10 min, mm-Fraction=97%, Content ofn-decane-insoluble components=89 wt %, Tm of n-decane-insolublecomponents=158° C., Intrinsic viscosity [η] of n-decane-insolublecomponents=2.3 dl/g

Sheet Molding Method:

The starting materials with composition ratios described in Tables 3-3-1and 3-3-2 were melt-kneaded with a 60-mmΦ extrusion sheet moldingmachine into a 500-μm thick sheet.

Evaluation Method for Whitening Resistance:

A dumbbell for tensile test in accordance with JIS K6301-2 was obtainedfrom the resulting sheet. The change in hue (L-value) was evaluated whenthe dumbbell was stretched by 5 mm or 10 mm.

ΔL=L-value (after stretch)−L-value (before stretch)

TABLE 3-3-1 Example Example Example Comparative 3-21 3-22 3-23 Example3-21 Propylene-based rPP(A3-1) 90 90 90 100 polymer Soft PEBR(B3) 10 5 5propylene/α-olefin random copolymer PER(b3-1) Non-crystalline PP(b3-2)Soft polymer SEBS(C3) 5 EBR(D3) 5 L(before stretch) 26.5 26.9 27.6 26.5ΔL(5 mm) 0.7 1.9 1.6 6.7 ΔL(10 mm) 19.5 27.5 22.4 49.4 ComparativeComparative Comparative Comparative Example 3-22 Example 3-23 Example3-24 Example 3-25 Propylene-based rPP(A3-1) 90 90 90 90 polymer SoftPEBR(B3) propylene/α-olefin random copolymer PER(b3-1) 10Non-crystalline 10 PP(b3-2) Soft polymer SEBS(C3) 10 EBR(D3) 10 L(beforestretch) 27.3 26.8 27.1 29.8 ΔL(5 mm) 3.8 0.7 1.1 4.2 ΔL(10 mm) 37.924.8 33.1 40.6 Note: Amount of each component blended is given in partsby weight

TABLE 3-3-2 Example Example Example Comparative 3-24 3-25 3-26 Example3-26 Propylene-based polymer bPP(A3-2) 90 90 90 100 Softpropylene/α-olefin PEBR(B3) 10 5 5 random copolymer PER(b3-1)Non-crystalline PP(b3-2) Soft polymer SEBS(C3) 5 EBR(D3) 5 L(beforestretch) 34.6 34.7 34.6 36.3 ΔL(5 mm) 0.9 2.0 1.5 28.7 ΔL(10 mm) 14.223.6 21.5 50.2 Comparative Comparative Comparative Comparative Example3-27 Example 3-28 Example 3-29 Example 3-30 Propylene-based polymerrPP(A3-2) 90 90 90 90 Soft propylene/α-olefin PEBR(B3) random copolymerPER(b3-1) 10 Non-crystalline 10 PP(b3-2) Soft polymer SEBS(C3) 10EBR(D3) 10 L(before stretch) 35.4 35.2 35.2 35.9 ΔL(5 mm) 10.3 2.4 17.219.4 ΔL(10 mm) 34.2 27.7 36.6 38.7 Note: Amount of each componentblended is given in parts by weight

The molded articles obtained from the propylene-based polymercompositions using PEBR (B3) related to the third aspect of inventionare excellent in whitening resistance.

<3-2> Evaluations for Cap Liner and Wrap Film Performance Examples 3-31and 3-32 and Comparative Examples 3-31 to 3-38

Cap liner performances were compared among PEBR (B3), PER (b3-1),non-crystalline PP (b3-2), SEBS (C3), EBR (D3), and rPP (A3-1) (Table3-4-1). Wrap film performances were also evaluated with films formedfrom these materials (Table 3-4-2). In Tables 3-4-1 and 3-4-2, the unitfor each component is parts by weight.

Evaluation Method for Cap Liner Performances:

Starting materials with the component ratios shown in Table 3-4-1 werekneaded by the same method as that in Example 3-1 to form pellets, whichwere molded into 0.3-mm or 2-mm thick sheets with a press moldingmachine (heating: 190° C. for 7 min, cooling: 15° C. for 4 min, coolingspeed: about −40° C./min).

Stretching Property Evaluation:

A film strip was cut out of the 0.3-mm thick sheet. This film wasstretched by 150% (45 mm (chuck-to-chuck distance after stretching)/30mm (chuck-to-chuck distance before stretching)×100) at a tensile speedof 20 mm/min with a tensile tester. Then the tensile stress wasreleased, and the residual strain was measured when the tensile stressbecame zero.

Residual strain=(100×(chuck-to-chuck distance at zero stress)/30)−100

Compression Property Evaluation:

In accordance with JIS K-6301, six 2-mm thick pressed sheets werestacked and compressed by 25% and kept at predetermined temperatures(23° C. and 70° C.) for 24 hr, and after the load was released, thethickness of the stack was measured. From the results, deformation after24-hr compression (permanent compression set) was calculated using thefollowing equation:

Permanent compression set=100×(thickness before test−thickness aftertest)/(thickness before test−thickness on compression).

Evaluation Method for Wrap Film Performances:

With a three-kind three-layer cast molding machine, was prepared amulti-layer film composed of a 20-μm thick film made of the compositionin Table 3-4-2 as an inner layer and a 5-μm thick layer made of LLDPE(density=915 kg/m³, MFR(230° C.)=7.2 g/10 min) on each of both the facesof the film.

The resulting film was stretched by 150% in a similar manner to theresidual strain evaluation, the whitening status of the film wasevaluated by visual observation.

Excellent: no whitening, Do: slight whitening, Poor: marked whitening

From the above 150%-stretched (1.5-times stretched) film, a dumbbell inaccordance with JIS K6781 was obtained and subjected to tensile test ata tensile speed of 200 m/min to evaluate the presence or absence ofyield point.

TABLE 3-4-1 Example Comparative Comparative Comparative Comparative 3-31Example 3-31 Example 3-32 Example 3-33 Example 3-34 Propylene-basedrPP(A3) 20 20 20 20 20 polymer Soft PEBR(B3) propylene/α-olefin 80random copolymer PER(b3-1) 80 Non- 80 crystalline PP(b3-2) Soft polymerSEBS(C3) 80 EBR(D3) 80 Residual strain % 22 22 37 20 26 Permanent % 2123 75 18 33 compression set (23° C.) Permanent % 63 94 86 98 99compression set (70° C.)

TABLE 3-4-2 Example Comparative Comparative Comparative Comparative 3-32Example 3-35 Example 3-36 Example 3-37 Example 3-38 Propylene-basedrPP(A3) 50 50 50 50 50 polymer Soft PEBR(B3) 50 propylene/α-olefinrandom copolymer PER(b3-1) 50 Non- 50 crystalline PP(b3-2) Soft polymerSEBS(C3) 50 EBR(D3) 50 Wrap film whitening Excellent Do Excellent DoPoor resistance Yield point status absent absent absent absent absent

The film made of the propylene-based polymer composition using PEBR (B3)of the third aspect of invention exhibits excellent stretching propertyand whitening resistance.

<Fourth Aspect of Invention> [Starting Materials]

(a) Isotactic Polypropylene (iPP)

Ethylene content=4.2 mol %, MFR=2.7 g/10 min, Melting point=135° C.,mmmm-Fraction=0.96

(b) Propylene/Ethylene/1-Butene Random Copolymer (PEBR)

Ethylene content=14.0 mol %, 1-Butene content=20 mol %, MFR=8.5 g/10min, Melting point=not observed (ΔH: less than 0.5 J/g), Molecularweight distribution (Mw/Mn)=2.0, mm-Fraction=92%

(PEBR was Prepared by the Method Described in WO 2004/87775.)

Specifically, PEBR was prepared as follows. Namely, in a 2000-mLpolymerization reactor fully purged with nitrogen, 917 mL of dry hexane,90 g of 1-butene, and 1.0 mmol of triisobutylaluminum were charged atnormal temperature, the inside temperature of the reactor was elevatedto 65° C., and propylene was introduced so that the inside pressure ofreactor increased to 0.77 MPa, and then ethylene was supplied so as toadjust the pressure to 0.79 MPa. To this reactor was added a toluenesolution in which 0.002 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corp.) had beencontacted, and the polymerization was conducted for 20 min while theinside temperature was kept at 65° C. and ethylene was supplied to keepthe inside pressure at 0.79 MPa. The polymerization was terminated byadding 20 mL of methanol, the pressure was released, and the polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 60.4 g of the desiredpolymer.

(c) Petroleum Resin (P-125, Available from Arakawa Chemical Industries,Ltd.)

Mn=820, Softening point measured with the ring-and-ball method=125° C.

(d) Propylene/1-Butene Copolymer (PBR)

1-Butene content=27 mol %, MFR=7.1 g/10 min, Melting point=73° C.,Molecular weight distribution (Mw/Mn)=2.1

(e) Ethylene/1-Butene Copolymer (EBR)

Density=870 kg/m³, Melting point=53° C., MFR(230° C.)=7.0 g/10 min,Mw/Mn=2.1

The properties of the above materials were measured by the followingmethods:

(1) Co-Monomer (Ethylene and 1-Butene) Contents

the contents were determined by ¹³C-NMR spectrum analysis.

(2) MFR

MFR at 230° C. under a load of 2.16 kg was measured in accordance withASTM D1238.

(3) Melting Point

In exothermic/endothermic curve measured with a DSC, the temperature atthe maximum melting peak in heating was counted as Tm. A sample loadedon an aluminum pan was heated to 200° C. at 100° C./min, kept at 200° C.for 5 min, cooled to −150° C. at 10° C./min, and heated at 10° C./minduring which the exothermic/endothermic curve was recorded.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Density

The density was measured by the method in accordance with ASTM D1505.

(6) Mn of Hydrocarbon Resins

The Mn was measured by GPC (gel permeation chromatography).

(7) Softening Point of Hydrocarbon Resins

The softening point was measured by the ring-and-ball method inaccordance with ASTM D36.

Examples 4-1 to 4-3, Reference Example 4-1, and Comparative Example 4-2Preparation of Oriented Film

Each starting material shown in Table 4-1 was kneaded with a 40-mmΦextruder and the resulting pellets were extruded at 230° C., with a castfilm molding machine, into a 250-μm thick single-layer film. In Table4-1, the unit for each component is parts by weight.

A 9-cm square sheet was cut out of the above film and drawn by 5 times(in molding direction of cast film, i.e., MD direction) and 1 time (inTD direction) with a benchtop biaxial film stretching machine.

Draw temperature was 80° C., pre-heating time was 90 sec, and draw speedwas 10 m/min. The film was air-cooled immediately after drawn.

TABLE 4-1 Reference Comparative Example Example Example Example Example4-1 4-2 4-3 4-1 4-2 iPP 80 80 80 80 80 PEBR 20 20 15 PBR 20 EBR 5 20P-125 15 15 15

The resulting films were evaluated on the following properties.

1. Heat Shrink Ratio

A specimen of 10 mm×100 mm (in draw direction) was cut out of theoriented film and immersed in hot water at 80° C. or 90° C. for 10 sec.Heat shrink ratio was obtained from the dimensional changes of the filmbefore and after the immersion, using equation (1).

[Mathematical 1]

100×{(dimension in draw direction before test)−(dimension in drawdirection after test)}/(dimension in draw direction after test)  (1)

2. Transparency

Internal haze (%) was measured with a digital haze/tubidimeter “NDH-20D”available from Nippon Denshoku Kogyo Co., Ltd.

3. Film Impact (F.I.)

The film impact was measured for a film sized 100 mm×100 mm at −10° C.using a film impact tester with a 0.5-inchΦ spherical impact head,available from Toyo Seiki Seisaku-sho Ltd.

4. Film Strength

Tensile strength at break (TS) was measured in the tensile test inaccordance with JIS K6781 (tensile direction was the same as the drawdirection of the film, and the tensile speed was 200 mm/min).

TABLE 4-2 Characteristics of oriented film Example Example ExampleReference Comparative 4-1 4-2 4-3 Example 4-1 Example 4-2 Shrink ratio(90° C.) % 19 25 25 16 18 Shrink ratio (80° C.) % 13 14 13 10 13Internal haze % 1.8 2.5 2.4 1.7 5.5 F.I. kJ/m 12.5 9.5 12.0 4.5 13.0 TSMPa 90 84 80 94 78

The above results clearly indicate that the films of the fourth aspectof invention have high heat shrink ratio, and also excellenttransparency and film impact resistance.

<Fifth Aspect of Invention>

The test methods for evaluation in Examples and Comparative Examples aredescribed below.

(i) Methods for Measuring Properties of Each Component (1) Melting Point(Tm), Crystallization Temperature (Tc), and Glass Transition Temperature(Tg)

In exothermic/endothermic curve measured with a DSC, the temperature atthe maximum exothermic peak on cooling was counted as Tc, thetemperature at the maximum melting peak on heating was counted as Tm,and the secondary transition point observed in the endothermic curvebetween −100° C. and 0° C. was counted as Tg.

In the above measurement, a sample loaded on an aluminum pan was heatedto 200° C. at 100° C./min, kept at 200° C. for 5 min, cooled to −150° C.at 20° C./min, and heated at 20° C./min during which theexothermic/endothermic curve was recorded.

(2) Melt Flow Rate (MFR)

MFR at 230° C. under a load of 2.16 kg was measured in accordance withASTM D1238.

(3) Co-Monomer (Ethylene, Propylene, and 1-Butene) Contents andMmmm-Fraction (Stereoregularity, Pentad Isotacticity)

The contents and mmmm-fraction were determined by ¹³C-NMR spectrumanalysis.

(4) mm-Fraction

The mm-fraction was measured by the method described in WO 2004/87775.

(5) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(6) Density

The density was measured in accordance with ASTM D1505.

(7) Shore a Hardness

The Shore A hardness was measured in accordance with JIS K6301 under thefollowing conditions.

A 2-mm thick sheet was prepared with a press molding machine. The scalewas read immediately after the pointer of a Type-A hardness testertouched the sheet.

(ii) Properties of Each Component

(A5-1) Isotactic Polypropylene-1 (rPP)

PP ter-polymer (propylene/ethylene/1-butene random copolymer) (Tm=140°C., MFR(230° C.)=7 g/10 min, mmmm-Fraction=96%, Mw/Mn=4.8) was used.

(A5-2) Isotactic Block Polypropylene-2 (bPP)

Propylene/ethylene block copolymer (Tm=158° C., MFR(230° C.)=1.3 g/10min, mmmm-Fraction=96%, Rubber content (n-decane-extractablefraction)=11 wt %, Ethylene content=10 mol %) was used.

(B5-1) Propylene/Ethylene/1-Butene Copolymer (PEBR)

Propylene/ethylene/1-butene copolymer (Ethylene content=14.0 mol %,1-Butene content=19 mol %, MFR(230° C.)=7 g/10 min, Tm=not observed (ΔH:less than 0.5 J/g), Mw/Mn=2.0, Shore A hardness=45, mm-Fraction=92%) wasused.

Specifically, PEBR was prepared as follows. Namely, in a 2000-mLpolymerization reactor fully purged with nitrogen, 917 mL of dry hexane,85 g of 1-butene, and 1.0 mmol of triisobutylaluminum were charged atnormal temperature, the inside temperature of reactor was elevated to65° C., and propylene was introduced so that the inside pressure ofreactor increased to 0.77 MPa, and then ethylene was supplied so as toadjust the pressure to 0.78 MPa. To this reactor was added a toluenesolution in which 0.002 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corp.) had beencontacted, and the polymerization was conducted for 20 min while theinside temperature was kept at 65° C. and ethylene was supplied to keepthe inside pressure at 0.78 MPa. The polymerization was terminated byadding 20 mL of methanol, the pressure was released, and the polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 60.4 g of PEBR.

(B5-2) Non-Crystalline PP

There was used a composition (Shore A hardness of the composition=61)obtained by melt-kneading 85 wt % of non-crystalline propylene/1-butenecopolymer (Melting point=not observed, 1-Butene content=3 mol %,mm-Fraction=11%, MFR=3 g/10 min) and 15 wt % of isotactichomopolypropylene (Melting point=160° C.)

(C5) Soft Polymer

Ethylene/1-butene copolymer (EBR) (Density=870 kg/m³, Tm=53° C.,MFR(230° C.)=7.2 g/10 min, Mw/Mn=2.1, Shore A hardness=71) was used.

(iii) Evaluation items for Examples 5-1 to 5-4 and Comparative Examples5-1 and 5-2

(1) Transparency

The diffuse transmission and total transmission were measured with adigital haze/tubidimeter “NDH-2000” available from Nippon Denshoku KogyoCo., Ltd. for each sheet in cyclohexanol to obtain internal haze usingthe following equation:

Internal haze=100×(Diffuse transmission)/(Total transmission).

(2) Scratch Resistance

Each sample was abraded using a “Gakushin” abrasion testing machineavailable from Toyo Seiki Seisaku-sho Ltd. equipped with a 45R SUS-madeabrasion indenter weighing 470 g whose tip was covered with a cottoncloth No. 10, under conditions of 23° C., the number of reciprocationsof 100 times, a reciprocation speed of 33 times/min, and a stroke of 100mm. The gloss retention percentage with abrasion, AGloss, was calculatedas follows. The larger AGloss is, the better the abrasion resistance is.

Gloss retention percentage=100×Gloss after abrasion/Gloss beforeabrasion

(3) Heat Resistance

The heat resistance was evaluated as Vicat softening temperature (JISK7206). Each resin composition with the component ratio described inTable 5-1 was re-molded into a 2-mm thick press-molded sheet(hot-pressed at 190° C., cooled at about −40° C./min with a chiller),which was used in the test.

(4) Mechanical Properties

In accordance with JIS K6301, yield stress (YS), elongation at yield (ELat YS), tensile strength at break (TS), elongation at break (EL), andYoung's modulus (YM) were measured for JIS #3 dumbbell with a spandistance of 30 mm at a tensile speed of 30 mm/min at 23° C.

(5) Permanent Compression Set (CS at 23° C. And 70° C.)

In accordance with JIS K6301, six 2-mm thick press-molded sheets werestacked and compressed by 25% and the permanent compression set after24-hr compression at 23° C. or 70° C. was evaluated using the followingequation. The smaller the value is, the more excellent the compressionset resistance is.

Permanent compression set=100×“strain after test” (thickness beforetest−thickness after test)/“strain” (thickness before test−thickness oncompression)

Example 5-1

The starting materials with the component ratio described in Table 5-1was melt-kneaded with a 40-mm0 single-screw extruder into pellets, whichwere molded into a 2-mm thick sheet with a press molding machine(heating: 90° C. for 7 min, cooling: 15° C. for 4 min, cooling speed:about −40° C./min). Items (1) to (5) above were evaluated for theresultant sheet. The results are shown in Table 5-1.

Examples 5-2 to 5-4 and Comparative Examples 5-1 and 5-2

Evaluation was made similarly to Example 5-1, except that each startingmaterial with the component ratio described in Table 5-1 was usedinstead of the composition in Example 5-1.

TABLE 5-1 Example Example Example Example Comparative Comparative 5-15-2 5-3 5-4 Example 5-1 Example 5-2 A5-1 rPP pbw 80 40 80 40 80 40 B5-1PEBR pbw 20 60 B5-2 pbw 20 60 non-crystalline PP C5 EBR pbw 20 60Transparency % 75 50 73 48 91 93 Scratch resistance % 90 77 93 85 62 7Heat resistance °C. 115 73 110 55 112 42 YS MPa 19 9 16 None 19 8 EL atYS % 11 20 11 None 7 9 TS MPa 30 25 22 11 19 12 EL % 530 590 480 560 370150 YM MPa 620 150 580 120 770 100 CS(23° C.) % 54 43 55 56 58 55 CS(70°C.) % 77 66 80 77 90 100 Note: pbw = parts by weight

(iv) Evaluation Items for Examples 5-11 and 5-12, and ComparativeExamples 5-21 and 5-22 (6) Mechanical Properties

Using specimens in accordance with ASTM 4, yield stress (YS), elongationat yield (EL at YS), tensile strength at break (TS), elongation at break(EL), and Young's modulus (YM) were determined at a tensile speed of 50mm/min (tensile direction=MD (mold) direction).

(7) Whitening Resistance on Drawing

Dumbbells for tensile test in accordance with JIS K6301-2 were obtainedfrom the sheets prepared. Each dumbbell was drawn by 5 mm or 10 mm, andthe change in hue (L-value in specular excluded method) was evaluatedusing the following equation. The smaller ΔL is, the more excellentwhitening resistance on drawing is.

ΔL=L-value (after drawn)−L-value (before drawn)

(8) Whitening resistance on folding

Each sheet prepared was folded at about 90° to evaluate the occurrenceof whitening.

Excellent: no whitening (whitening disappears when unfolded)

Poor: whitening (whitening remains even after unfolded)

(9) Wrinkle Resistance

Each sheet prepared was heat-sealed at 190° C. under 0.2 MPa for 3 seconto a substrate, which was a 200-μm thick polyethylene sheet (LLDPE,density=900 kg/m³), to obtain a specimen, which was folded at 90° toevaluate the appearance.

Excellent: no creases develop after folded,

Poor: creases (including sheet peeling off) develop.

Example 5-11

The starting materials with the component ratio described in Table 5-2were molded into a 500-μm thick sheet at 230° C. with a sheet-moldingmachine. Items (6) to (9) above were evaluated for this sheet. Theresults are shown in Table 5-2.

Example 5-12, Comparative Examples 5-21 and 5-22

Evaluation was made similarly to Example 5-11 except that each startingmaterial with the component ratio described in Table 5-2 was usedinstead of the composition in Example 5-11.

TABLE 5-2 Example Example Comparative Comparative 5-11 5-12 Example 5-21Example 5-22 A5-2 bPP pbw 90 90 100 90 B5-1 PEBR pbw 10 B5-2 pbw 10non-crystalline PP C5 EBR pbw 10 YS MPa 23 22 26 23 EL at YS % 10 10 7 8TS MPa 38 36 40 39 EL % 620 640 610 640 YM MPa 1010 980 1300 1060Whitening ΔL(5 mm) 1 2 28 3 resistance on ΔL(10 mm) 16 19 50 34 drawingWhitening Occurrence Excellent Excellent Poor Poor resistance on offolding Whitening Wrinkle resistance Appearance Excellent Excellent PoorExcellent evaluation Note: pbw = parts by weight

<Sixth Aspect of Invention> (i) Components (A6) to (F6) (A6)Propylene-Based Polymer

(A6-1) Isotactic Random Polypropylene (rPP)

Propylene/ethylene/1-butene random copolymer (Tm=140° C., MFR(230° C.)=7g/10 min, mmmm-Fraction=0.96, Mw/Mn=4.8) was used.

(A6-2) Isotactic Block Polypropylene (bPP)

Propylene/ethylene block copolymer (Tm=160° C., MFR(230° C.)=23 g/10min, Ethylene content=9 wt %, n-Decane-soluble content=12%) was used.

(B6) Propylene-Based Polymer (B6-1) Propylene/1-Butene Copolymer (PBR)

Propylene/1-butene copolymer (MFR=7 g/10 min, Tm=75° C., 1-Butenecontent=26 mol %, Mw/Mn=2.1, crystallinity (by WAXD)=28%,mm-Fraction=90%) was used.

(PBR was prepared by the method described in WO 2004/87775.)

(B6-2) Propylene/Ethylene/1-Butene Copolymer (PEBR)

Propylene/ethylene/1-butene random copolymer (MFR=8.5 g/10 min, Tm=notobserved (ΔH: less than 0.5 J/g), Ethylene content=14 mol %, 1-Butenecontent=20 mol %, Mw/Mn=2.0, Shore A hardness=38, crystallinity (byWAXD)=5% or less, mm-Fraction=92%, prepared by the method described inWO 2004/87775) was used. Specifically, PEBR was prepared as follows. Ina 2000-mL polymerization reactor fully purged with nitrogen, 917 mL ofdry hexane, 90 g of 1-butene, and 1.0 mmol of triisobutylaluminum werecharged at normal temperature, the inside temperature of the reactor waselevated to 65° C., propylene was introduced so that the inside pressureof the reactor was increased to 0.77 MPa, and then the inside pressurewas regulated at 0.79 MPa with ethylene. Into the reactor was added atoluene solution in which 0.002 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corp.) had beencontacted, and polymerization was conducted for 20 min while the insidetemperature was kept at 65° C. and the inside pressure was kept at 0.79MPa by adding ethylene. The polymerization was terminated by adding 20mL of methanol, the pressure was released, and the polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 60.4 g of the desiredpolymer.

(C6) Elastomer (C6-1) Styrene-Based Elastomer (SEBS)

SEBS “G1650” (product name) available from Kraton Polymers LLC was used.

(C6-2) Ethylene/1-Butene Copolymer (EBR)

Ethylene/1-butene copolymer (Density=870 kg/m³, Tm=53° C., MFR(230°C.)=7 g/10 min, Mw/Mn=2.1) was used.

(D6) Inorganic Filler

Magnesium hydroxide (Mg(OH)₂, “KISUMA 5P” (product name) available fromKyowa Chemical Industry Co., Ltd.) was used.

(E6) Oil

Paraffin oil (“PW-90” (product name) available from Idemitsu Kosan Co.,Ltd., Kinematic viscosity at 40° C.=90 cSt) was used.

(F6) Graft-Modified Polymer

Maleic anhydride-grafted ethylene/1-butene copolymer (F6-2) was preparedusing ethylene/1-butene copolymer (F6-1) below.

TABLE 6-1 Properties of ethylene/1-butene copolymer (F6-1) (F6-1)Density (kg/m³) 885 MFR(g/10 min) (190° C., under a load of 2.16 kg) 0.5Mw/Mn 2.1 B-value 1.05

Ten kilograms of ethylene/1-butene copolymer (F6-1) produced using ametallocene catalyst, whose properties are shown in Table 6-1, and asolution containing 50 g of maleic anhydride and 3 g of di-tert-butylperoxide in 50 g of acetone were blended in a Henschel mixer.

The resulting blend was supplied to the hopper of a single-screwextruder (40-mmΦ, L/D=26) and extruded at a resin temperature of 260° C.at an extrusion speed of 6 kg/hr into a strand, which was water-cooledand pelletized to obtain maleic anhydride-grafted ethylene/1-butenecopolymer (F6-2).

After unreacted maleic anhydride was extracted with acetone from theresulting maleic anhydride-grafted ethylene/1-butene copolymer (F6-2),the amount of maleic anhydride grafted in this copolymer was measured tobe 0.43 wt %.

(G6) Propylene-Based Polymer Composition (Corresponding toPropylene-Based Polymer Composition (G′6))

Propylene/1-butene copolymer (PBR) (B6-1) as propylene-based polymer(B6) and maleic anhydride-grafted ethylene/1-butene copolymer (F6-2)above were kneaded in the ratio in Table 6-2 at 190° C. with a Laboplast-mill available from Toyo Seiki Seisaku-sho, Ltd. to preparecomposition (G6).

TABLE 6-2 (F6-1) Maleic anhydride-grafted (B6-1) PBR ethylene/1-butenecopolymer 16 (wt %) 5 (wt %)

(ii) Methods for Measuring Properties for Each Component

The properties of each component were measured as follows.

(1) Co-Monomer (Ethylene and 1-Butene) Content and mmmm-Fraction(Stereoregularity, Pentad Isotacticity)

The content and mmmm-fraction were determined by ¹³C-NMR spectrumanalysis.

(2) Melt Flow Rate (MFR)

In exothermic/endothermic curve measured with a DSC, the peak toptemperature of melting peak with ΔH of 1 J/g or higher observed onheating was counted as Tm.

A sample loaded on an aluminum pan was heated to 200° C. at 100° C./min,kept at 200° C. for 5 min, cooled to −150° C. at 10° C./min, and heatedto 200° C. at 10° C./min during which the exothermic/endothermic curvewas recorded.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Density

The density was measured by the method in accordance with ASTM D 1505.

(6) Crystallinity

The crystallinity was estimated from a wide-angle X-ray diffractionprofile recorded with an X-ray diffractometer “RINT2500” available fromRigaku Corp., using CuKα X-ray source.

(7) Shore a Hardness

The Shore A hardness was measured in accordance with JIS K6301 under thefollowing conditions.

A sheet was prepared with a press molding machine. The scale was readimmediately after the pointer of a Type-A hardness tester touched thesheet.

(iii) Evaluation items for Examples 6-1 and 6-2, Comparative Examples6-1 and 6-2, and Reference Examples 6-1 and 6-2

(1) Tensile Strength at Break (TS), Elongation at Break (EL), andFlexibility (YM)

In accordance with JIS K7113-2, tensile strength at break (TS),elongation at break (EL), and Young's modulus (YM) were measured for a 2mm-thick press-molded sheet.

(2) Scratch Resistance (Gloss Retention Percentage)

Each specimen was abraded using a “Gakushin” abrasion testing machineavailable from Toyo Seiki Seisaku-sho Ltd. equipped with a 45R SUS-madeabrasion indenter weighing 470 g whose tip was covered with cotton clothNo. 10, under conditions of 23° C., the number of reciprocations of 100times, a reciprocation speed of 33 times/min, and a stroke of 100 mm.The gloss retention percentage with abrasion, AGloss, was calculated asfollows. The larger AGloss is, the better the abrasion resistance is.

Gloss retention percentage=100×Gloss after abrasion/Gloss beforeabrasion

Example 6-1

The starting materials with the component ratio in Table 6-3 werekneaded with a Labo plast-mill (available from Toyo Seiki Seisaku-sho,Ltd.) and molded into a 2-mm thick sheet with a press molding machine(heating: 190° C. for 7 min, cooling: 15° C. for 4 min, cooling speed:about −40° C./min). Items (1) and (2) above were evaluated with thissheet. The results are shown in Table 6-3.

Example 6-2, Comparative Examples 6-1 and 6-2, and Reference Examples6-1 and 6-2

Evaluation was made similarly to Example 6-1 except that the startingmaterialswith the component ratio in Table 6-3 were used instead of thecomposition in Example 6-1.

Note that the composition used in Reference Example 6-1 has the sameresin component as that in Example 6-1, and contains no Mg(OH)₂., andthat the composition used in Reference Example 6-2 has the same resincomponent as that in Comparative Example 6-1, and contains no Mg(OH)₂.

TABLE 6-3 Examples 6-1 and 6-2, Comparative Examples 6-1 and 6-2, andReference Examples 6-1 and 6-2 Reference Example Example ReferenceComparative Comparative Example 6-1 6-1 6-2 Example 6-2 Example 6-1Example 6-2 (A6-1) rPP wt % 20 14 6 (B6-2) PEBR wt % 80 56 24 (C6-2) EBRwt % 100  70 30 (D6) Mg(OH)₂ wt % 30 70 30 70 Mg(OH)₂ blended wt %  0 3070  0 30 70 TS MPa 12   7.5 4.5 11   5.2 3.8 EL % 800< 800< 560 800<800< 20 YM MPa  16< 18 91 13 24 169 Gloss retention % 90 65 46 10 15 25percentage

For compositions containing inorganic filler (magnesium hydroxide), thepropylene-based resin compositions of the present invention are superiorto the ethylene-based resin compositions used in Comparative Examples intensile strength at break, elongation at break, and scratch resistance.In addition, the propylene-based resin compositions have excellentbalance of mechanical strength and flexibility, as shown by lessincrease in Young's modulus.

(iv) Evaluation items for Examples 6-3 to 6-5 and Comparative Example6-3

(3) Tensile Strength at Break (TS) and Elongation at Break (EL)

The tensile strength at break and elongation at break were evaluatedwith a 2-mm thick press-molded sheet in accordance with JIS K-6301-3.

(4) Scratch Resistance (Taber Abrasion)

With a Taber type abrasion tester in accordance with JIS K7204, theabrasion weight loss (mg) was obtained from the weight change of eachspecimen before and after the abrasion test using a truck wheel (CS-17)under the conditions of rotation speed of 60 rpm, 1000 test cycles, andload of 1000 g.

(5) Low-Temperature Brittleness Temperature (Btp)

The low-temperature brittleness temperature was measured in accordancewith ASTM D746.

(6) D Hardness (HD-D)

The D hardness was measured in accordance with ASTM D 2240.

Example 6-3

The starting materials with the ratio in Table 6-4 were kneaded with aLabo plast-mill (available from Toyo Seiki Seisaku-sho, Ltd.) and moldedinto a 2-mm thick sheet with a press molding machine (heating: 190° C.for 7 min, cooling: 15° C. for 4 min, cooling speed: about −40° C./min).Items (3) to (6) above were evaluated with this sheet. The results areshown in Table 6-4.

Examples 6-4 and 6-5 and Comparative Example 6-3

Evaluation was made similarly to Example 6-3 except that the startingmaterials were changed as described in Table 6-4.

TABLE 6-4 Examples 6-3 to 6-5 and Comparative Example 6-3 ExampleExample Example Comparative 6-3 6-4 6-5 Example 6-3 (A6-1) rPP wt % 4(A6-2) bPP wt % 30 30 30 30 (B6-1) PBR wt % 20 15 (B6-2) PEBR wt % 16(C6-1) SEBS wt % 5 (C6-2) EBR wt % 20 (D6) Mg(OH)₂ wt % 50 50 50 50 TSMPa 19 14 12 12 EL % 310 210 210 50 Abrasion mg 118 119 99 127 weightloss Low- ° C. 2 −3 −8 −10 temperature brittleness D hardness 61 60 5157

The propylene-based resin compositions of the sixth aspect of inventionare superior to the conventional compositions used in the comparativeExamples containing polypropylene (bPP) and elastomer particularly inelongation at break (EL) and scratch resistance (abrasion weight loss).In particular, as shown in Example 6-5, it is confirmed that use ofpropylene/ethylene/1-butene copolymer (PEBR) (B6-2) improves flexibilityand also provides better low-temperature brittleness property.

Example 6-6

Evaluation was made similarly to Example 6-3 except that the startingmaterials were changed to those described in Table 6-5.

TABLE 6-5 Example 6-6 Example 6-6 (A6-2) bPP wt % 30 (B6-1) PBR wt % 20(D6) Mg(OH)₂ wt % 50 (E6) Oil parts by weight *1 5 TS MPa 17 EL % 360Abrasion weight loss mg 82 Low-temperature brittleness ° C. −27 Dhardness 57 Feeling by hands No stickiness *1 Amount relative to 100parts by weight of the total of components (A6-2), (B6-1), and (D6).

As shown in Example 6-6, it is confirmed that additional use of oilprovides the propylene-based resin composition of the sixth aspect ofinvention with particularly excellent low-temperature brittlenessproperty and scratch resistance.

Example 6-7

Evaluation was made similarly to Example 6-3 except that the startingmaterials were changed to those described in Table 6-6.

TABLE 6-6 Example 6-7 Example 6-7 (A6-2) bPP wt % 32 (B6-1) PBR wt % 16(D6) Mg(OH)₂ wt % 52 (F6-2) graft-modified parts by weight *1 5 polymerTS MPa 19 EL % 280 Abrasion weight loss mg 90 D hardness 58 Feeling byhands No stickiness *1 Amount relative to 100 parts by weight of thetotal of components (A6-2), (B6-1), and (D6)

As shown in Example 6-7, it is confirmed that additional use ofgraft-modified polymer provides the propylene-based resin composition ofthe present invention with particularly excellent scratch resistance.

Example 6-8

Evaluation was made similarly to Example 6-3 except that the startingmaterials were changed to those described in Table 6-7.

TABLE 6-7 Example 6-8 Example 6-8 (A6-2) bPP parts by 32 weight (D6)Mg(OH)₂ parts by 52 weight (G6) Polymer blend: parts by 21(B6-1)PBR/(F6-2)graft-modified weight polymer = 16/5 (weight ratio) TSMPa 20 EL % 300 Abrasion weight loss mg 81 D hardness 58 Feeling byhands No stickiness

As shown in Example 6-8, it is confirmed that the propylene-based resincomposition of the sixth aspect of invention exhibits more excellentscratch resistance when produced using the melt-kneaded blend(propylene-based polymer composition).

<Seventh Aspect of Invention>

(i) Properties of propylene-based polymer (A7), propylene-based polymer(B7), ethylene/α-olefin copolymer (C7), and ethylene/polar monomercopolymer (D7) used in Examples and Comparative Examples were measuredas follows.

(1) Density

The density was measured in accordance with ASTM D1505 at 23° C.

(2) MFR

The MFR was measured in accordance with ASTM D1238 at predeterminedtemperatures. MFR(230° C.) represents the value at 230° C. under a loadof 2.16 kg. MFR₂ represents the value at 190° C. under a load of 2.16kg. MFR₁₀ represents the value at 190° C. under a load of 10 kg.

(3) B-value, Tαβ Tαα intensity ratio

The B-value and Tαβ were determined by ¹³C-NMR.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was determined by gel permeation chromatography usingo-dichlorobenzene as a solvent at 140° C.

(5) Ethylene Content and Propylene Content

The ethylene content and propylene content were determined by ¹³C-NMR.

(6) Melting Point

The melting point was determined with a differential scanningcalorimeter (DSC). In exothermic/endothermic curve measured with a DSC,the temperature at the maximum melting peak on heating was counted asTm. A sample loaded on an aluminum pan was heated to 200° C. at 100°C./min, kept at 200° C. for 5 min, cooled to −150° C. at 10° C./min, andheated at 10° C./min during which the exothermic/endothermic curve wasrecorded.

(ii) The properties of components (A7), (B7), (C7), and (D7) used in thepresent invention are described below.

(1) Propylene Polymer (B7-1): Propylene/Ethylene/1-Butene RandomCopolymer (PEBR)

Ethylene content=14.0 mol %, 1-Butene content=20 mol %, MFR(230° C.)=8.5g/10 min, Melting point=not observed (AH: less than 0.5 J/g), Molecularweight distribution (Mw/Mn)=2.0, mm-Fraction=92%

The propylene/ethylene/1-butene copolymer used for the present inventionwas prepared, for example, by the method in accordance with Examples 1eto 5e of WO 2004/87775. Specifically, the copolymer was prepared asfollows. Namely, in a 2000-mL polymerization reactor fully purged withnitrogen, 917 mL of dry hexane, 90 g of 1-butene, and 1.0 mmol oftriisobutylaluminum were charged at normal temperature, the insidetemperature of the reactor was elevated to 65° C., and propylene wasintroduced so that the inside pressure of the reactor increased to 0.77MPa, and then ethylene was supplied to adjust the inside pressure to0.79 MPa. To this reactor was added a toluene solution in which 0.002mmol of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corp.) had beencontacted, and the polymerization was performed for 20 min while theinside temperature was kept at 65° C. and the inside pressure was keptat 0.79 MPa by supplying ethylene. The polymerization was terminated byadding 20 mL of methanol, the pressure was released, and the polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 60.4 g of the desiredcopolymer.

Propylene-based polymer (B7-2): propylene/1-butene copolymer (PBR)

1-Butene content=4 mol %, MFR(230° C.)=3.0 g/10 min, Melting point=notobserved, Molecular weight distribution (Mw/Mn)=2.0, Shore Ahardness=61, mm-Fraction=15%

(2) Propylene-Based Polymer (A7): Isotactic Polypropylene (iPP)

Ethylene content=2.0 mol %, 1-Butene content=1.5 mol %, MFR(230° C.)=7g/10 min, Melting point=140° C.

(3) Ethylene/α-Olefin Copolymer (C7): Ethylene/1-Butene Copolymer (EBR)

The copolymer was synthesized as shown in Production Example 1 below.

Production Example 7-1 Preparation of Catalyst Solution

In 5 mL of toluene was dissolved 18.4 mg of triphenylcarbenium(tetrakispentafluorophenyl)borate to prepare a 0.004-M toluene solution.In 5 mL of toluene was dissolved 1.8 mg of[dimethyl(t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)si lane]titaniumdichloride to prepare a 0.001-M toluene solution. Prior to startingpolymerization, 0.38 mL of the toluene solution of triphenylcarbenium(tetrakispentafluorophenyl)borate and 0.38 mL of the toluene solution of[dimethyl(t-butylamido) (tetramethyl-η⁵-cyclopentadienyl)silane]titanium dichloride were mixed with 4.24 mL of toluene to prepare 5mL of a toluene solution so that, in the polymerization solution, theconcentration of triphenylcarbenium (tetrakispentafluorophenyl)boratebecame 0.002 mM (relative to boron) and that of [dimethyl(t-butylamido)(tetramethyl-1₁ ⁵-cyclopentadienyl)si lane] titanium dichloride became0.0005 mM (relative to titan).

[Preparation of Ethylene/1-Butene Copolymer (C7)]

In a 1.5-L SUS autoclave with stirring propellers fully purged withnitrogen, 750 mL of heptane was charged at 23° C. Into the autoclave, 10g of 1-butene and 120 mL of hydrogen were charged with ice-cooling whilethe stirring propellers rotated. The autoclave was heated to 100° C.,and ethylene was introduced so that the total pressure became 0.6 MPa.When the inside pressure of the autoclave reached 0.6 MPa, 1.0 mL of1.0-mM/mL hexane solution of triisobutylaluminum (TIBA) was injectedwith positive pressure of nitrogen, and then 5 mL of the catalystsolution prepared above was injected into the autoclave with positivepressure of nitrogen to start polymerization. The polymerization wasperformed for 5 min while the temperature inside the autoclave wasregulated at 100° C. and the inside pressure was kept at 0.6 MPa bydirectly supplying ethylene. At 5 min after start of polymerization, 5mL of methanol was pumped into the autoclave to terminatepolymerization, the autoclave was released to atmospheric pressure, and3 L of methanol was added to the reaction solution. The resultingpolymer containing solvent was dried at 130° C. for 13 hr under 600 Torrto obtain 10 g of ethylene/1-butene copolymer (C7). The properties ofethylene/1-butene copolymer (C7) obtained are shown in Table 7-1.

TABLE 7-1 Production Example 7-1 Properties of polymer Ethylene/1-butenecopolymer (C7) Density (kg/m³) 885 Melt flow rate (MFR₂) 1.2 Mw/Mn 2.1MFR₁₀/MFR₂ 10.0 B-value 1.0 Tαβ/Tαα 0.3

(4) Ethylene/Polar Monomer Copolymer (D7): Ethylene/Vinyl AcetateCopolymer (EVA)

“EV460” (TM, available from DU PONT-MITSUI POLYCHEMICALS

Co., Ltd.),

Vinyl acetate content=19 wt %

Density (ASTM D1505, 23° C.)=0.94 g/cm³

Melt flow rate (MFR₂(190° C.))(ASTM D1238, 2.16-kg load, 190° C.)=2.5g/10 min

(iii) Properties of Crosslinked Foams were Evaluated as Follows.

(1) Specific Gravity

The specific gravity was measured in accordance with JIS K7222.

(2) Permanent Compression Set

The permanent compression set test was performed in accordance with JISK6301 at 50° C. for 6 hr with 50%-compression to determine permanentcompression set (CS).

-   -   (3) Tear strength Tear strength test was performed in accordance        with BS 5131-2.6 at a tensile speed of 10 mm/min to obtain tear        strength.

(4) Asker C Hardness

The Asker C hardness was measured in accordance with “Spring-typehardness test, Type-C test method” described in Appendix 2 of JISK7312-1996.

(5) Impact Resilience

A steel ball of 15 g was fallen from a height of 50 cm (L₀) and theheight rebound (L) was measured at 23° C. and 40° C. to obtain impactresilience using equation, impact resilience (%)=L/L₀×100

(6) Abrasion Resistance

Akron abrasion test was conducted in accordance with JIS K6246 under aload of 6 lbs at an angle of 15° with a total rotation number of 3000 ata rotation speed of 35 rpm, and the weight change of specimen wasmeasured to abrasion resistance.

(7) Adhesion Strength of Laminate (7-1) Treatment for SecondaryCrosslinked Foam

At first, surfaces of a secondary crosslinked foam were water-washedusing a surfactant and dried at room temperature for 1 hr. Thissecondary crosslinked foam was immersed in methylcyclohexane for 3 minand then dried in an oven at 60° C. for 3 min.

An ultraviolet-curable primer (“GE258H1”™ available from Great EasternResins Industrial Co., Ltd.) was thinly applied with a brush on thefoam, and dried in an oven at 60° C. for 3 min. The foam was irradiatedwith ultraviolet light on an irradiation system (EPSH-600-3S UVirradiation system, available from GS Corp.) with three 80-W/cmhigh-pressure mercury lamps installed perpendicular to the travelingdirection, while traveled in a plane 15 cm beneath the light source at aconveyer speed of 10 m/min.

After that, an auxiliary primer (“GE6001L”™ available from Great EasternResins Industrial Co., Ltd., mixed with 5 wt % of curing agent “GE366S”)was thinly applied using a brush and dried in an oven at 60° C. for 3min.

Then, an adhesive (“98H”™ available from Great Eastern Resins IndustrialCo., Ltd., mixed with 4 wt % of curing agent “GE348”) was thinly appliedwith a brush and dried in an oven at 60° C. for 5 min.

Finally, the above adhesive-coated secondary crosslinked foam waslaminated with a synthetic leather sheet of polyurethane (PU) treated asdescribed below and they were press-bonded under 20 kg/cm² for 10 sec.

(7-2) Treatment for PU Synthetic Leather Sheet

Surface of a PU synthetic leather sheet was washed with methyl ethylketone and dried at room temperature for 1 hr. On the surface, anauxiliary primer (“GE6001L”™ available from Great Eastern ResinsIndustrial Co., Ltd., mixed with 5 wt % of curing agent “GE366S”) wasthinly applied with a brush and dried in an oven of 60° C. for 3 min.Then, an adhesive (“98H”™ available from Great Eastern Resins IndustrialCo., Ltd., mixed with 4 wt % of curing agent “GE348”) was thinly appliedwith a brush and dried in an oven of 60° C. for 5 min.

(7-3) Peeling Test

The adhesion strength of the above press-bonded laminate was evaluatedat 24 hr after preparation as follows.

Namely, the laminate was cut into 1-cm wide specimens. At one end ofeach specimen, the two layers were separated and pulled at a tensilespeed of 200 mm/min in directions making an angle of 180° to measure thepeeling strength. The peeling test was conducted for five specimens, andthe average value is shown as adhesion strength in Table 7-2. Thepeeling status of specimen was observed by eyes.

Example 7-1

A mixture containing 80 parts by weight of propylene/ethylene/1-butenecopolymer (B7-1), 20 parts by weight of isotactic polypropylene (A7),and 100 parts by weight of ethylene/1-butene copolymer (C7) relative to100 parts by weight of the total of (B7-1)+(A7); further, relative to100 parts by weight of the total of (B7-1), (A7), and (C7), 3.0 parts byweight of zinc oxide, 0.7 parts by weight of dicumyl peroxide (DCP), 0.2parts by weight of triallyl isocyanurate (TAIC) (“M-60”(product name,containing 60% TAIC), available from Nippon Kasei Chemical Co., Ltd.)(0.12 parts by weight relative to TAIC), 0.4 parts by weight of1,2-polybutadiene, and 3.5 parts by weight of azodicarbonamide waskneaded with a kneader at a preset temperature of 100° C. for 10 min.The mixture was further kneaded with rolls at a roll surface temperatureof 100° C. for 10 min and molded into a sheet.

The resulting sheet was placed in a press mold and pressed and heatedunder 150 kg/cm² at 155° C. for 30 min to obtain a primary crosslinkedfoam. The press mold sized 15 mm thick, 150 mm long, and 200 mm.

This primary crosslinked foam was compression-molded under 150 kg/cm² at155° C. for 10 min to obtain a secondary crosslinked foam, which sized15 mm thick, 160 mm long, and 250 mm wide.

For this secondary crosslinked foam, evaluation was performed by theabove methods on specific gravity, permanent compression set, tearstrength, Asker C hardness, impact resilience, and abrasion resistance.Further, the adhesion strength of a laminate composed of the foam and asynthetic leather sheet of polyurethane (PU) was measured by the abovemethod, and the peeling status was observed by eyes. The results areshown in Table 7-2.

Example 7-2

A secondary crosslinked foam was prepared and properties thereof wereevaluated similarly to Example 7-1, except that the amount ofethylene/1-butene copolymer (C7) was changed from 100 parts by weight to200 parts by weight and that the mixture used here contained, relativeto 100 parts by weight of the total of (B7-1), (A7), and (C7), 3.0 partsby weight of zinc oxide, 0.7 parts by weight of dicumyl peroxide (DCP),0.2 parts by weight of triallyl isocyanurate (TAIC) (“M-60” (productname, containing 60% TAIC), available from Nippon Kasei Chemical Co.,Ltd.) (0.12 parts by weight relative to TAIC), 0.4 parts by weight of1,2-polybutadiene, and 3.7 parts by weight of azodicarbonamide. Theresults are shown in Table 7-2.

Example 7-3

A secondary crosslinked foam was prepared and properties thereof wereevaluated similarly to Example 7-1, except that 100 parts by weight ofethylene/1-butene copolymer (C7) was changed to 100 parts by weight ofethylene/1-butene copolymer (C7) and 100 parts by weight ofethylene/vinyl acetate copolymer (D7), and that the mixture used hereincontained, relative to 100 parts by weight of the total of (A7-1), (B7),(C7), and (D7), 3.0 parts by weight of zinc oxide, 0.7 parts by weightof dicumyl peroxide (DCP), 0.2 parts by weight of triallyl isocyanurate(TRIC) (“M-60” (product name, containing 60% TAIC), available fromNippon Kasei Chemical Co., Ltd.) (0.12 parts by weight relative toTAIC), 0.4 parts by weight of 1,2-polybutadiene, and 3.7 parts by weightof azodicarbonamide. The results are shown in Table 7-2.

Example 7-4

A secondary crosslinked foam was prepared and properties thereof wereevaluated similarly to Example 7-1, except that ethylene/1-butenecopolymer (B7-1) in Example 1 was replaced by propylene/1-butenecopolymer (B7-2), and that the mixture used herein contained, relativeto 100 parts by weight of the total of (B7-2), (A7), and (C7), 3.0 partsby weight of zinc oxide, 0.7 parts by weight of dicumyl peroxide (DCP),0.2 parts by weight of triallyl isocyanurate (TRIC) (“M-60” (productname, containing 60% TAIC), available from Nippon Kasei Chemical Co.,Ltd.) (0.12 parts by weight relative to TAIC), 0.4 parts by weight of1,2-polybutadiene, and 3.7 parts by weight of azodicarbonamide. Theresults are shown in Table 7-2.

Comparative Example 7-1

A secondary crosslinked foam was prepared and properties thereof wereevaluated similarly to Example 7-1, except that the amount ofpropylene/ethylene/1-butene copolymer (B7-1) was changed from 80 partsby weight to 0 parts by weight and the amount of isotactic polypropylene(A7) was changed from 20 parts by weight to 0 parts by weight, and thatthe mixture used herein contained, relative to 100 parts by weight ofethylene/1-butene copolymer (C7), 3.0 parts by weight of zinc oxide, 0.7parts by weight of dicumyl peroxide (DCP), 0.2 parts by weight oftriallyl isocyanurate (TRIC) (“M-60” (product name, containing 60%TAIC), available from Nippon Kasei Chemical Co., Ltd.) (0.12 parts byweight relative to TAIC), 0.4 parts by weight of 1,2-polybutadiene, and4.0 parts by weight of azodicarbonamide. The results are shown in Table7-2.

Comparative Example 7-2

A secondary crosslinked foam was prepared and properties thereof wereevaluated similarly to Comparative Example 7-1, except that 100 parts byweight of ethylene/1-butene copolymer (C7) was changed to 100 parts byweight of ethylene/vinyl acetate copolymer (D7). The results are shownin Table 7-2.

TABLE 7-2 Example Example Example Example Comparative Comparative 7-17-2 7-3 7-4 Example 7-1 Example 7-2 PEBR B7-1 80 80 80 PBR B7-2 80 iPPA7 20 20 20 20 EBR C7 100 200 100 100 100 EVA D7 100 100 Additive (phr)(Amount relative to 100 parts by weight of the total of B7-1, B7-2, A7,C7, and D7 above) ZnO 3.0 St/A 1.0 TiO2 3.0 DCP 0.70 TAIC M60 0.201,2-polybutadiene 0.40 ADCA (AC#3) 3.5 3.7 3.7 3.7 4.0 4.0 Properties ofcrosslinked foams Hardness 44 45 49 43 46 52 Specific gravity 0.17 0.150.14 0.18 0.15 0.15 Permanent compression set % 49 54 56 61 57 66 Tearstrength N/cm 85 87 80 71 86 60 Impact resilience % 38 49 46 49 65 50Abrasion resistance g 0.075 0.081 0.088 0.078 0.092 0.178 (weight loss)Adhesion strength N/cm 2.8 2.7 2.6 2.5 2.5 1.9 Gel fraction % 79 81 8381 86 84 Peeling status Partly Partly Partly Partly Partly Partly peeled(*) peeled (*) peeled (*) peeled (*) peeled (*) peeled (*) (*) Thelaminate was separated at the interface between the foam layer and thePU synthetic leather sheet.

<Eighth Aspect of Invention> [Starting Materials]

(A8) Isotactic Polypropylene (rPP):

Propylene/ethylene/1-butene random copolymer (Tm=140° C., MFR(230° C.)=7g/10 min, mmmm-Fraction=0.96, Mw/Mn=4.8) was used.

(B8) Propylene/Ethylene/1-Butene Copolymer (PEBR)

Ethylene content=14.0 mol %, 1-Butene content=20 mol %, MFR=8.5 g/10min, Melting point=not observed (AH: less than 0.5 J/g), Molecularweight distribution (Mw/Mn)=2.0, Shore A hardness=38, mm-Fraction=92%

(PEBR was prepared by the method described in WO 2004/87775.)Specifically, PEBR was prepared as follows. In a 2000-mL polymerizationreactor fully purged with nitrogen, 917 mL of dry hexane, 90 g of1-butene, and 1.0 mmol of triisobutylaluminum were charged at normaltemperature, the temperature in the reactor was elevated to 65° C.,propylene was introduced so that the pressure in the reactor wasincreased to 0.77 MPa, and then ethylene was supplied so as to thepressure became 0.79 MPa. Into the reactor was added a toluene solutionin which 0.002 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride and 0.6 mmol (relative to aluminum) ofmethylaluminoxane (available from Tosoh Finechem Corp.) had beencontacted, and polymerization was conducted for 20 min while the insidetemperature was kept at 65° C. and the inside pressure was kept at 0.79MPa by adding ethylene. The polymerization was terminated by adding 20mL of methanol, the pressure was released, and the polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. under vacuum for 12 hr to yield 60.4 g of PEBR.

(Y8) Silane Coupling Agent (VTMOS) Vinyltrimethoxysilane, available fromDow Corning Toray Co., Ltd.

(D8) Ethylene/1-Butene Copolymer (EBR)

Density=870 kg/m³, Melting point=53° C., MFR(230° C.)=7.0 g/10 min,Mw/Mn=2.1

The properties of the above materials were measured by the followingmethods.

(1) Co-Monomer (Ethylene and 1-Butene) Contents, and mmmm-Fraction(Stereoregularity: Pentad Isotacticity)

The contents and mmmm-fraction were determined by ¹³C-NMR spectrumanalysis.

(2) MFR

MFR at 230° C. under a load of 2.16 kg was measured in accordance withASTM D1238.

(3) Melting Point

In exothermic/endothermic curve measured with a DSC, the temperature atwhich the maximum melting peak appeared on heating was counted as Tm. Asample loaded on an aluminum pan was heated to 200° C. at 100° C./min,kept at 200° C. for 5 min, cooled to −150° C. at 10° C./min, and heatedat 10° C./min during which the exothermic/endothermic curve wasrecorded.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Density

The density was measured by the method described in ASTM D1505.

[Evaluation Items] Tensile Strength at Break (TS) and Flexibility:

In accordance with JIS K7113-2, tensile strength at break (TS) andYoung's modulus (YM) were measured for a 2-mm thick press-molded sheet.

Transparency (Haze) (Internal Haze)

Measurement was performed with a digital haze/tubidimeter of “NDH-2000”available from Nippon Denshoku Kogyo Co., Ltd. using a 1.0-mm thickpress-molded sheet in cyclohexanol to calculate haze from the followingequation:

Haze (%)=100×(Diffuse transmission)/(Total transmission).

Heat Resistance (TMA)

In accordance with JIS K7196, a TMA curve was measured for a 2-mm thicksheet using a 1.8-mmΦ flat-ended needle under a load of 2 kgf/cm² at aheating speed of 5° C./min. The temperature (° C.) at which the needlepenetrated into the specimen was determined.

Adhesion Strength to Glass and PET

A 0.6-mm thick sheet was hot-press bonded (200° C., 5 min) to a glassplate (4 mm thick) and a PET film (“Lumirror”™ available from TorayIndustries, Inc., 100 μm thick), respectively. The peeling strength ofthe laminate was evaluated at −10° C. and then at room temperature.

Excellent: Firmly bonded, not easy to peel

Do: Bonded, but peelable

Poor: Not bonded

Shore a Hardness

The Shore A hardness was measured in accordance with JIS

K6301. (Measurement conditions) A sheet was prepared with a pressmolding machine. The scale was read immediately after the pointer of aType-A hardness tester touched the sheet.

Example 8-1

A mixture of 20 parts by weight of isotactic polypropylene (A8) (rPP),80 parts by weight of propylene/ethylene/1-butene copolymer (B8) (PEBR),and 1.5 parts by weight of silane coupling agent (Y8) was kneaded with aLabo plast mill at 190° C. for 5 min. The resulting resin compositionwas molded, using a press molding machine, into a 0.6-mm or 2-mm thicksheet, which was used to evaluate the above items.

Comparative Example 8-1

Relative to 100 parts by weight of isotactic polypropylene (A8) (rPP),1.5 parts by weight of silane coupling agent (Y8) was blended. Theresultant resin composition was evaluated by methods similar to those inExample 8-1.

Comparative Example 8-2

Relative to 100 parts by weight of ethylene/1-butene copolymer (D8)(EBR), 1.5 parts by weight of silane coupling agent (Y8) was blended.The resulting resin composition was evaluated by methods similar tothose in Example 8-1.

TABLE 8-1 Example Comparative Comparative 8-1 Example 8-1 Example 8-2(A8) iPP 20 100 (B8) PEBR 80 (D8) EBR 100 (Y8) VTMOS 1.5 1.5 1.5 Tensilestrength at 14.5 35.5 9.5 break (MPa) Modulus in tension 14 1020 18(MPa) Internal haze (%) 4.2 8.3 4.7 TMA(° C.) 117.2 139.5 78.5 Peelingstrength (to Excellent Poor Excellent glass, −10° C.) Peeling strength(to Excellent Excellent Excellent glass, 23° C.) Peeling strength (toExcellent Do Excellent PET, −10° C.) Peeling strength (to ExcellentExcellent Excellent PET, 23° C.)

<Ninth Aspect of Invention> [Evaluation Items] Haze (Internal Haze)

Measurement was performed with a digital haze/tubidimeter “NDH-2000”available from Nippon Denshoku Kogyo Co., Ltd. for a 1.0-mm thickpress-molded sheet in cyclohexanol to calculate haze using the followingequation:

Haze (%)=100×(Diffuse transmission)/(Total transmission).

Light transmittance (Trans)

The light transmittance was measured for a 1.0-mm thick sheet. Trans iscalculated using the following equation:

Trans (%)=100×(total transmitted light intensity)/(incident lightintensity).

Heat resistance (TMA)

In accordance with JIS K7196, a TMA curve was measured for a 2-mm thicksheet using a 1.8-mmΦ flat-ended needle under a load of 2 kgf/cm² at aheating speed of 5° C./min. The temperature (° C.) at which the needlepenetrated into the sheet was determined.

Mechanical Properties (Tensile Strength at Break and Modulus in Tension)

Tensile strength at break (TS) and Young's modulus (YM) were measured inaccordance with JIS K7113-2 for a 2-mm thick press-molded sheet.

Adhesion Strength to Glass

A 0.6-mm thick sheet was hot-press bonded to a glass plate with a pressmolding machine (150° C., 10 min, 0.2 MPa). The adhesion strength ofthis laminate was measured with a tensile tester (peeling speed: 300mm/min, peeling width (sample width): 1.5 cm, T-peel test method).

Shore a Hardness

The Shore A hardness was measured in accordance with JIS K6301.(Measurement conditions) A sheet was prepared with a press moldingmachine. The scale was read immediately after the pointer of a Type-Ahardness tester touched the sheet.

[Starting Materials Used for the Ninth Aspect]

(A9) Isotactic Polypropylene (iPP)

Ethylene content=3.0 mol %, 1-Butene content=1.0 mol %, MFR(230° C.)=7g/10 min, Melting point=140° C.

(B9) Propylene/ethylene/1-butene copolymer (PEBR)

Ethylene content=14.0 mol %, 1-Butene content=20 mol %, MFR(230° C.)=8.5g/10 min, Melting point=not observed (AH: less than 0.5 J/g), Molecularweight distribution (Mw/Mn)=2.0, Shore A hardness=37, mm-Fraction=92%

The propylene/ethylene/1-butene copolymer used in the present inventioncan be prepared, for example, by a method similar to Examples 1e to 5eof WO 2004/87775.

In Examples here, specifically, the copolymer was produced in accordancewith the method used for producing propylene/butene/ethylene copolymer(B8) in Examples of the eighth aspect.

(C9) Ethylene/Vinyl Acetate Copolymer (EVA)

Density=950 kg/m³, Vinyl acetate content=28 wt %, MFR(190° C.)=15 g/10min, Melting point=71° C.

(D9) Ethylene/1-Butene Copolymer (EBR)

Density=870 kg/m³, Melting point=53° C., MFR(230° C.)=7.0 g/10 min,Mw/Mn=2.1

(Y9) Silane Coupling Agent (VTMOS)

Vinyltrimethoxysilane, available from Dow Corning Toray

Co, Ltd.

(Z9) Organic peroxide (PH25B)

Dialkyl peroxide (“PERHEXA 25B”™, available from NOF Corp.)

(Z9-2) Auxiliary (TRIC)

Triallyl isocyanurate (TRIC) (“M-60” (product name), TRIC content=60%,available from Nippon Kasei Chemical Co., Ltd.), 0.2 parts by weight(0.12 parts by weight relative to TRIC)

[Measurement Methods for Properties of the Above Starting Materials] (1)Co-Monomer (Ethylene and 1-Butene) Contents

The contents were determined by ¹³C-NMR spectrum analysis.

(2) MFR

MFR at 190° C. or 230° C. under a load of 2.16 kg was measured inaccordance with ASTM D1238.

(3) Melting Point

In exothermic/endothermic curve measured with a DSC, the temperature atwhich the maximum melting peak appeared on heating was counted as Tm. Asample loaded on an aluminum pan was heated to 200° C. at 100° C./min,kept at 200° C. for 5 min, cooled to −150° C. at 10° C./min, and heatedat 10° C./min during which the exothermic/endothermic curve wasrecorded.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Density

The density was measured by the method in accordance with ASTM D1505.

Example 9-1

The starting materials shown in Table 9-1 were melt-kneaded with asingle-screw extruder (extrusion temperature: 220° C.). The resultantmelt-kneaded material was molded into a sheet (0.6 mm, 1 mm, or 2 mmthick) with a press molding machine (heating temperature: 190° C.,heating time: 5 min, cooling speed: −40° C./min). The above propertieswere evaluated for this sheet, which was a solar cell-sealing sheet. Theresults are shown in Table 9-1.

Example 9-2

A specimen of solar cell-sealing sheet was prepared from the startingmaterials (containing PH25B) shown in Table 9-1 by a similar method tothat in Example 9-1. The above properties were evaluated for thisspecimen. The results are shown in Table 9-1.

Example 9-3

A specimen of solar cell-sealing sheet was prepared from the startingmaterials (containing PH25B and TRIC) shown in Table 9-1 by a similarmethod to that in Example 9-1. The above properties were evaluated forthis specimen. The results are shown in Table 9-1.

Comparative Example 9-1

A specimen of solar cell-sealing sheet was prepared and above propertiesthereof were evaluated with the starting materials shown in Table 9-1 bya similar method to that in Example 9-1. The results are shown in Table9-1.

Comparative Example 9-2

A specimen of solar cell-sealing sheet was prepared and above propertiesthereof were evaluated with the starting materials shown in Table 9-1 bya similar method to that in Example 9-1. The results are shown in Table9-1.

TABLE 9-1 Examples and Comparative Examples Example Example ExampleComparative Comparative 9-1 9-2 9-3 Example 9-1 Example 9-2 (A9) iPP(pbw) 20 20 20 (B9) PEBR (pbw) 80 80 80 (C9) EVA (pbw) 100 (D9) EBR(pbw) 100 (Y9) VTMOS (pbw) 2 2 2 2 2 (Z9) PH25B (pbw) 0.09 0.09 (Z9-2)TAIC (pbw) 0.2 Crosslinking None None None None None Boiled 0 0 0 0 0hexane-insoluble content (wt %) Haze (%) 3.5 3.7 3.3 3.2 4.2 Trans (%)91 90 92 91 90 TMA (° C.) 117 113 115 77 80 Tensile strength 14 7 9 10 9at break (MPa) Modulus in 14 13 16 20 18 tension (MPa) Adhesion 6 12 1920 20 strength to glass (N/cm) Note pbw: parts by weight

<Tenth Aspect of Invention> [Measurement Methods]

In Examples and Comparative Examples below, the properties ofelectrical/electronic element-sealing sheets were evaluated by thefollowing measurement methods.

Flexibility

In accordance with JIS K6301, Shore A hardness was measured. A 2-mmthick press-molded sheet was prepared from each composition by heatingat 190° C. and then cooling at 40° C./min and used for measurement. InExamples, the composition forming layer (II-10) in the sheet was used,while in Comparative Examples, the composition forming the single-layersheet was used.

Transparency (Internal Haze):

Diffuse transmission and total transmission were measured with a digitalhaze/tubidimeter “NDH-2000” available from Nippon Denshoku Kogyo Co.,Ltd. for each sheet in cyclohexanol. Internal haze was calculated usingthe following equation:

Internal haze (%)=100×(Diffuse transmission)/(Total transmission).

Transparency (Light Transmittance)

Each composition was hot-pressed into a sheet (160° C., 2 atm, 10 min)while the sheet was protected with PET (“Lumirror”™, available fromToray Industries) to prevent surface roughness, which might affect theevaluation. After the sheet was air-cooled, the PET film was removed toobtain a specimen (0.4 mm thick). With this specimen, transmittance wasmeasured with a digital haze/tubidimeter “NDH-2000” available fromNippon Denshoku Kogyo Co., Ltd. Transmittance is represented by thefollowing equation:

Transmittance (%)=100×(total transmitted light intensity)/(incidentlight intensity).

Heat resistance (TMA)

In Examples, layer (II-10) in the sheet was used, while in ComparativeExamples the single-layer sheet was used. A TMA curve was measured inaccordance with JIS K7196 using a 1.8-mmΦ flat-ended needle under a loadof 2 kgf/cm² at a heating speed of 5° C./min. The temperature (° C.) atwhich the needle penetrated into the layer or sheet was determined.

Adhesion Strength to Glass and Appearance:

Layer (I-10) in the sheet in Examples, or the single-layer sheet inComparative Examples, was hot-press bonded to a 4-mm thick glass plateunder two different conditions (condition 1: 150° C., 2 atm, 10 min;condition 2: 160° C., 2 atm, 10 min). Peeling strength at roomtemperature of the laminate was evaluated as follows.

A: Firmly bonded, not easy to peel

B: Bonded, but peelable

C: Not bonded

Permanent Compression Set:

In accordance with JIS K6301, six 2-mm thick press-molded sheets werestacked and compressed by 25%, and the stack was kept under this load ata predetermined temperature (23° C. or 70° C.) for 24 hr, and then thestack was freed from the load and its thickness was measured. From theresults of measurement, the residual strain (permanent compression set)was calculated using the following equation:

Residual strain (%)=100×(“thickness before test”−“thickness aftertest”)/(“thickness before test”−“thickness on compression”).

[Starting Materials]

The species and properties of resins used to prepare specimens inExamples and Comparative Examples are as follows.

(A10) Isotactic polypropylene (rPP)

Propylene/ethylene/1-butene copolymer (Melting point (Tm)=140° C., Meltflow rate (MFR) (230° C.)=7 g/10 min, Isotactic pentad fraction(mmmm-fraction)=0.96, Molecular weight distribution (Mw/Mn)=4.8,Ethylene content=2.0 mol %, 1-Butene content=1.5 mol %) was used.

(B10) Propylene/Ethylene/1-Butene Copolymer (PEBR)

Propylene/ethylene/1-butene copolymer prepared in a similar method tothat described in Examples of WO 2004/87775 was used (Ethylenecontent=14.0 mol %, 1-Butene content=20 mol %, Melt flow rate (MFR)(230° C.)=8.5 g/10 min, Melting point (Tm)=not observed (AH: less than0.5 J/g), mm-Fraction=92%, Molecular weight distribution (Mw/Mn)=2.0,Shore A hardness=38).

Specifically, PEBR was prepared as follows. In a 2000-mL polymerizationreactor fully purged with nitrogen, 917 mL of dry hexane, 90 g of1-butene, and 1.0 mmol of triisobutylaluminum were charged at normaltemperature, the temperature in the reactor was elevated to 65° C.,propylene was introduced so that the pressure of the reaction system wasincreased to 0.77 MPa, and then the pressure was regulated at 0.79 MPawith ethylene. Into this reactor was added a toluene solution in which0.002 mmol of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fl uorenylzirconium dichlorideand 0.6 mmol (in terms of aluminum) of methylaluminoxane (available fromTosoh Finechem Corp.) had been contacted, and polymerization wasconducted for 20 min while the inside temperature was kept at 65° C. andthe inside pressure was kept at 0.79 MPa by adding ethylene. Thepolymerization was terminated by adding 20 mL of methanol, the pressurewas released, and the polymer was precipitated from the polymerizationsolution in 2 L of methanol and dried at 130° C. under vacuum for 12 hrto yield 60.4 g of PEBR.

(C10) Ethylene/Vinyl Acetate Copolymer (EVA)

Ethylene/vinyl acetate copolymer (Ethylene content=89 mol % (determinedby FT-IR), Shore A hardness=79, Melt flow rate (MFR) (190° C.)=15 g/10min) was used.

(D10) Ethylene/1-Butene Copolymer (EBR)

Ethylene/1-butene random copolymer (Melt flow rate (MFR) (190° C.)=15g/10 min, Density=870 kg/m³, Ethylene content=85 mol %, Shore Ahardness=72) was used.

(E10) Ethylene/Methacrylic Acid Copolymer (E(M)AA)

Ethylene/methacrylic acid copolymer (Methacrylic acid content=12 wt %(determined by FT-IR), Melt flow rate (MFR) (190° C.)=14 g/10 min) wasused.

(Y10) Silane Coupling Agent

3-Methacryloxypropyltrimethoxysilane available from Dow Corning TorayCo., Ltd. was used.

(Z10) Peroxide

DCP (dicumyl peroxide) available from ARKEMA YOSHITOMI, LTD. was used.

Measurement Methods for Properties of the Above Source Materials (1)Co-Monomer (Ethylene and 1-Butene) Contents

The contents were determined by ¹³C-NMR spectrum analysis.

(2) MFR

The MFR was measured in accordance with ASTM D1238 at 190° C. or 230° C.under a load of 2.16 kg.

(3) Melting Point

In exothermic/endothermic curve measured with a DSC, the temperature atwhich the maximum melting peak appeared on heating was counted as Tm. Asample loaded on an aluminum pan was heated to 200° C. at 100° C./min,kept at 200° C. for 5 min, cooled to −150° C. at 0° C./min, and heatedat 10° C./min during which the exothermic/endothermic curve wasrecorded.

(4) Molecular Weight Distribution (Mw/Mn)

The Mw/Mn was measured by GPC (gel permeation chromatography) usingo-dichlorobenzene as a solvent at 140° C.

(5) Density

The density was measured by the method in accordance with ASTM D1505.

(6) Shore A Hardness

The Shore A hardness was measured in accordance with JIS K6301 under thefollowing conditions. (Measurement conditions) A sheet was prepared witha press molding machine. The scale was read immediately after thepointer of a Type-A hardness tester touch the sheet.

Example 10-1

Layer (II-10) (thickness: 300 μm, extrusion temperature: 190° C.) wasprepared from a thermoplastic composition (permanent compression set at23° C.: 20%, permanent compression set at 70° C.: 61%) containing 20parts by weight of isotactic polypropylene (A10) (rPP) and 80 parts byweight of propylene/ethylene/1-butene copolymer (B10) (PEBR). Layer(I-10) (thickness: 100 μm, extrusion temperature: 120° C.) was preparedfrom 100 parts by weight of ethylene/vinyl acetate copolymer (C10)(EVA), 1.5 parts by weight of silane coupling agent (Y10), and 1.0 partby weight of peroxide (Z10). Thus a multilayer sheet(electrical/electronic element-sealing sheet) composed of these layerswas obtained.

For the resulting sheet, the above measurements were performed. Theresults are shown in Table 10-1.

Example 10-2

Layer (II-10) (thickness: 300 μm, extrusion temperature: 190° C.) wasprepared from a thermoplastic composition (permanent compression set at23° C.: 20%, permanent compression set at 70° C.: 61%) containing 20parts by weight of isotactic polypropylene (A10) (rPP) and 80 parts byweight of propylene/ethylene/1-butene copolymer (B10) (PEBR). Layer(I-10) (thickness: 100 μm, extrusion temperature: 130° C.) was preparedfrom 100 parts by weight of ethylene/1-butene copolymer (D10) (EBR), 1.5parts by weight of silane coupling agent (Y10), and 1.0 part by weightof peroxide (Z10). Thus, a multilayer sheet (electrical/electronicelement-sealing sheet) composed of these layers was obtained.

For the resulting sheet, the above measurements were performed. Theresults are shown in Table 10-1.

Comparative Example 10-1

A single-layer sheet (thickness: 400 μm, extrusion temperature: 130° C.)was obtained from 100 parts by weight of ethylene/vinyl acetatecopolymer (C10) (EVA).

For the resulting sheet, the above measurements were performed. Theresults are shown in Table 10-1.

Comparative Example 10-2

A single-layer sheet (thickness: 400 μm, extrusion temperature: 130° C.)was obtained from 100 parts by weight of ethylene/methacrylic acidcopolymer (E10)(E(M)AA).

For the resulting sheet, the above measurements were performed. Theresults are shown in Table 10-1.

Reference Example 10-3

A single-layer sheet (thickness: 400 μm, extrusion temperature: 190° C.,permanent compression set at 23° C.: 24%, permanent compression set at70° C.: 66%) was obtained from 20 parts by weight of isotacticpolypropylene (A10) (rPP) and 80 parts by weight ofpropylene/ethylene/1-butene copolymer (B10) (PEBR) (100 parts by weightin total), 1.5 parts by weight of silane coupling agent (Y10), and 0.03parts by weight of peroxide (Z10).

For the resulting sheet, the above measurements were performed. Theresults are shown in Table 10-1.

TABLE 10-1 Example Example Comparative Comparative Reference 10-1 10-2Example 10-1 Example 10-2 Example 10-3 Shore A 74 74 76 ≧95 74 Internalhaze % 1.2 1.6   0.9 1.6 2.4 Light % 94 93 94 90 94 transmittance TMA °C. 118 119  60> 88 118 Adhesion to Condition 1 A A A A C glass Condition2 A A A A B

INDUSTRIAL APPLICABILITY

The thermoplastic resin composition of the present invention isexcellent in rubber elasticity, that is, permanent compression set aswell as mechanical properties. In particular, the composition exhibitssmall temperature dependence in permanent compression set, keepingrubber elasticity even at high temperature, so that the composition issuitably used for automobile interior and exterior components,construction and building components, home electric appliancecomponents, cap liners, gaskets, convenience goods (grips), and others.

The thermoplastic resin composition of the present invention andcrosslinked product thereof have flexibility well-balanced with scratchresistance and whitening resistance and are kneadable at lowtemperature. So that, these are suitably used for automobile interiorand exterior components, construction and building components, homeelectric appliance components, cap liners, gaskets, convenience goods(grips), and others.

The propylene-based polymer composition of the present invention isexcellent in whitening resistance, impact resistance, scratchresistance, flexibility, transparency, mechanical strength, andstretching property. Molded articles made of the polymer composition arewidely used in industrial applications as blow-molded articles,injection-molded articles, extrusion-molded articles (films and sheets),inflation-molded articles, tubes, and others.

The film of the present invention has a high heat-shrink ratio and alsois excellent in flexibility, transparency, impact resistance, andstretching property, so that the film is suitably used asheat-shrinkable films and others. The thermoplastic resin composition ofthe present invention is suitably used to produce films having a highheat-shrink ratio and excellent flexibility, transparency, impactresistance, and stretching property.

The polyolefin decorative sheet of the present invention is excellent inflexibility, scratch resistance, abrasion resistance, mechanicalstrength (tensile strength at break), heat resistance, whiteningresistance on stretching, whitening resistance on folding, wrinkleresistance, water resistance, and compression set resistance. Therefore,the film is not particularly limited on its applications, and suitablyused for home electric appliances and furniture such as TV cabinets,stereo-speaker boxes, video cabinets, and various storage furniture andunified furniture; housing members such as doors, door frames, windowsashes, crown, plinth, and opening frames; furniture members such asdoors of kitchen and storage furniture; construction and buildingmaterial such as floor material, ceiling material, and wall paper;automobile interior material; home electric appliances; stationery;office goods; and others.

The propylene-based resin composition of the present invention containsinorganic filler at a high content, and is excellent in, as well asflexibility, mechanical strength, elongation at break, and scratchresistance. In addition, the propylene-based resin composition of thepresent invention can be widely used for fire-retardant molded articlesincluding electrical wires and construction and building materialsbecause of high content of inorganic filler.

The foaming material (X7) of the present invention provides foams havinglow specific gravity and permanent compression set (CS) as well asexcellent tearing strength, low resilience, and good scratch resistance.Such foams can be used for footwear and footwear components. Thefootwear components include, for example, shoe soles, shoe mid soles,inner soles, soles, and sandals.

The resin composition of the present invention exhibits goodheat-bondability to inorganic materials, such as metals and glass, andother plastics, and also high peeling strength in a wide range oftemperature. In addition, the resin composition of the present inventionis excellent in flexibility, heat resistance, transparency, andmechanical strength, and hence suitably used as a raw material forvarious applications.

The solar cell-sealing sheet of the present invention exhibits excellentheat resistance even though not cross linked. The solar cell-sealingsheet of the present invention can eliminate the crosslinking step fromsolar cell production processes, and also facilitate recycle of solarcells.

1. A thermoplastic resin composition (X2) comprising (A2), (B2), (C2),(D2), and (E2) below: 5 to 95 wt % of a propylene/α-olefin copolymer(B2) whose melting point is not higher than 100° C. or not observed whenmeasured with a differential scanning calorimeter (DSC); 5 to 95 wt % ofa styrene-based elastomer (C2); 0 to 90 wt % of an isotacticpolypropylene (A2); 0 to 70 wt % of an ethylene/α-olefin copolymer (D2)whose density is in the range of 0.850 to 0.910 g/cm³, wherein the totalof (A2), (B2), (C2), and (D2) is 100 wt %; and a softener (E2) in anamount of 0 to 400 parts by weight relative to 100 parts by weight ofthe total of (A2), (B2), (C2), and (D2).
 2. The thermoplastic resincomposition (X2) according to claim 1, wherein the propylene/α-olefincopolymer (B2) is a copolymer of propylene and at least one C₄-C₂₀α-olefin.
 3. The thermoplastic resin composition (X2) according to claim1, wherein the propylene/α-olefin copolymer (B2) is a propylene/1-butenecopolymer whose molecular weight distribution (Mw/Mn) is 3 or less asmeasured by gel permeation chromatography (GPC).
 4. The thermoplasticresin composition (X2) according to claim 1, wherein thepropylene/α-olefin copolymer (B2) is obtained by polymerization using ametallocene catalyst.
 5. A crosslinked product of the thermoplasticresin composition (X2) obtained by crosslinking the thermoplastic resincomposition (X2) according to claim
 1. 6. A molded article made of thethermoplastic resin composition (X2) according to claim
 1. 7. A moldedarticle made of the crosslinked product according to claim
 5. 8. Amolded article made of a crosslinked product of the thermoplastic resincomposition (X2) obtained by crosslinking the thermoplastic resincomposition (X2) according to claim 1, obtained by further crosslinkinga molded article made of the thermoplastic resin composition (X2)according to claim 1.